Conference Proceedings - 3rd International Conference on Methods

Transcription

Wrocław University of Technology
Faculty of Chemistry
PROCEEDINGS
OF THE IIIrd
INTERNATIONAL CONFERENCE
ON METHODS AND MATERIALS
FOR SEPARATION PROCESSES
SEPARATION SCIENCE
– THEORY AND PRACTICE 2015
6-10 SEPTEMBER, 2015, KARPACZ, POLAND
Oficyna Wydawnicza Politechniki Wrocławskiej
Wrocław 2015
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,
without the prior permission in writing from the publisher.
© Copyright by Oficyna Wydawnicza Politechniki Wrocławskiej, Wrocław 2015
OFICYNA WYDAWNICZA POLITECHNIKI WROCŁAWSKIEJ
Wybrzeże Wyspiańskiego 27, 50-370 Wrocław
http://www.oficyna.pwr.wroc.pl
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ISBN 978-83-7493-902-7
Druk i oprawa: EXPOL, P. Rybiński, J. Dąbek, sp.j., ul. Brzeska 4, 87-800 Włocławek
Tel. 54 232 37 23, e-mail: sekretariat@expol.home.pl
IIIrd
INTERNATIONAL CONFERENCE
ON METHODS AND MATERIALS
FOR SEPARATION PROCESSES
SEPARATION SCIENCE
– THEORY AND PRACTICE 2015
KARPACZ
POLAND
6-10 SEPTEMBER 2015
organized by:
Wrocław University of Technology
INTERNATIONAL ADVISORY BOARD
Prof. S. D. Alexandratos, USA
Prof. J. L. Cortina, Spain
Prof. G. Cote, France
Prof. E.S. Dragan, Romania
Prof. A.K. Frolkova, Russia
Prof. E. Guibal, France
Prof. A. de Haan, The Netherlands
Prof. Z. Hubicki, Poland
Prof. N. Kabay, Turkey
Dr D. J. Malik, UK
Prof. K. Ohto, Japan
Prof. M. Streat, UK
Prof. F. Svec, USA
Prof. G. Sulaberidze, Russia
Prof. V.V. Tepliakov, Russia
Prof. K. Yoshizuka, Japan
ORGANIZING COMMITTEE
Prof. Andrzej W. Trochimczuk - Chairman
Dr Anna Jakubiak-Marcinkowska
Dr Sylwia Ronka
Joanna Czulak
Małgorzata Kujawska
Magdalena Legan
Address:
Wroclaw University of Technology
Wybrzeże Wyspiańskiego 27,
50-370 Wrocław, Poland
Phone: +4871 320 3173
Fax: +4871 320 2152
CONFERENCE PROGRAM
6.09.
Sun
7.09.
Mon
8.09.
Tue
9.09.
Wed
10.09.
Thu
9:00 - 9:15
Opening
9:15 - 9:55 L1
9:15 - 9:55 L3
9:15 - 9:55 L5
09:30
D. Dreisinger
B. Schuur
M. Whitcombe
Bus departure
for Wrocław
9:55 - 10:35 L2
9:55 - 10:35 L4
9:55 - 10:35 L6
10:35 - 10:55 S1
10:35 - 10:55 S5
10:35 - 10:55 S9
K. Omelchuk
M. RegelRosocka
S. Nishihama
10:55 - 11:20
10:55 - 11:20
10:55 - 11:20
Coffee Break
Coffee Break
Coffee Break
11:20 - 11:40 S2
11:20 - 11:40 S6
11:20 - 11:40 S10
A. Gabor
M.G. Bogdanov
K. Staszak
11:40 - 12:00 S3
11:40 - 12:00 S7
11:40 - 12:00 S11
K. Yoshizuka
M. Baczyńska
P. Kowalczuk
12:00 - 12:20 S4
12:00 - 12:20 S8
12:00 - 12:20 S12
J. Gęga
M. Przewoźna
A. Trochimczuk
A. Chagnes
D. Antos
B. Gawdzik
12:20 - 12:30
Closing Remarks
12:30 - 14:00
Lunch
12:30 - 14:00
Lunch
12:30 - 14:00
Lunch
15:00 - 19:00
15:00 - 17:00
14:00 - 18:30
Registration
Poster Session
Excursions
19:00 - 21:00
18:30 - 19:45
19:30 - 01:30
18:30 - 19:45
Welcome
Reception
Dinner
Banquet
Dinner
5
6
I. LECTURES
L1
David Dreisinger (University of British Columbia, Canada)
19
NEW
PROSPECTS
FOR
ADVANCEMENT
OF
COPPER
HYDROMETALLURGY FOR THE TREATMENT OF HIGH GRADE
COPPER ORES AND CONCENTRATES
L2
A. Chagnes, A. Dartiguelongue, D. Beltrami, E. Provost, W. Furst, 22
G. Cote (Chimie ParisTech - Institut de Recherche de Chimie Paris,
France)
NEW HIGHLIGHTS ON URANIUM RECOVERY FROM PHOSPHORIC
ACID: FROM FUNDAMENTAL SCIENCE TO PROCESS
L3
E. Reyhanitash, S. R. A. Kersten, B. Schuur (University of Twente, 23
The Netherlands)
VOLATILE FATTY ACID RECOVERY FROM FERMENTATION BROTHS
L4
Dorota Antos (Rzeszów University of Technology, Poland)
DOWNSTREAM PROCESS – HOW TO CAPTURE A PROTEIN?
L5
Michael J. Whitcombe, Sergey A. Piletsky, Elena V. Pileska, 26
Antonio Guerreiro, Kal Karim (University of Leicester, UK)
MOLECULARLY IMPRINTED POLYMER NANOPARTICLES PREPARED
BY THE SOLID-PHASE APPROACH: PLASTIC ANTIBODIES FOR
SEPARATIONS, ASSAYS AND SENSORS
L6
Barbara Gawdzik (UMCS Lublin, Poland)
ROLE OF POLYMERIC MATERIALS IN SEPARATION SCIENCE
24
27
7
II. SHORT LECTURES
S1
K. Omelchuk, M. Haddad, G. Cote, A. Chagnes
31
NEW EXTRACTANTS FOR THE RECOVERY OF COBALT AND NICKEL
ACIDIC CHLORIDE SOLUTIONS
S2
Andreea Gabor, Corneliu Mircea Davidescu, Adina Negrea, 32
Mihaela Ciopec, Petru Negrea, Cătălin Ianași
LANTHANUM REMOVAL FROM AQUEOUS SOLUTIONS USING
FLORISIL
IMPREGNATED
WITH
TETRABUTYLAMMONIUM
DIHYDROGEN PHOSPHATE
CANCELLED
S3
Kazuharu Yoshizuka, Shuhei Tanaka, Hironori Murakami,
Syouhei Nishihama
PRECIOUS METAL RECOVERY FROM THE WASTES
USING ION EXCHANGE METHOD
S4
Jerzy Gęga, Paulina Otrembska
38
SEPARATION OF NICKEL(II) AND CADMIUM(II) IONS WITH IONEXCHANGE AND MEMBRANE PROCESSES
S5
Magdalena Regel-Rosocka, Agnieszka Krzyżkowska, Maciej 42
Wiśniewski
REACTIVE EXTRACTION AS A METHOD FOR REMOVAL OF LOW
MOLECULAR CARBOXYLIC ACIDS FROM FERMENTATION BROTH
S6
Milen G. Bogdanov, Rozalina Keremedchieva, Ivan Svinyarov
46
IONIC LIQUIDS AS ALTERNATIVE SOLVENTS FOR SELECTIVE
EXTRACTION OF SECONDARY METABOLITES FROM PLANT
MATERIALS: A CASE STUDY
S7
M. Baczyńska, M. Regel-Rosocka, T. M. Coll, A. Fortuny, A. M. 47
Sastre, M. Wiśniewski
PHOSPHONIUM IONIC LIQUIDS AS METAL ION CARRIERS
THROUGH POLYMER INCLUSION MEMBRANES (PIM) AND
SUPPORTED LIQUID MEMBRANES (SLM)
S8
Marta Przewoźna, Piotr Gajewski, Mariusz B. Bogacki 51
INFLUENCE OF COMPOSITION OF MEMBRANE ON TRANSPORT OF
SELECTED ORGANIC ACIDS THROUGH POLYMER INCLUSION
MEMBRANE
S9
Syouhei Nishihama, Yasuhiro Tsutsumi, Takeru Mino, 55
Kazuharu Yoshizuka
NANOFILTRATION OF TETRAMETHYLAMMONIUM HYDROXIDE BY
USING MFI-TYPE ZEOLITE COATED MEMBRANE
8
36
S10
Katarzyna Staszak, Roksana Drzazga, Daria Wieczorek
57
MICELLAR-ENHANCED ULTRAFILTRATION FOR REMOVAL OF
METAL IONS FROM AN AQUEOUS SOLUTION
CANCELLED
S11
Przemyslaw B. Kowalczuk, Jan Zawala, Anna Niecikowska, 61
Kazimierz Malysa
FLOTATION, HYDROPHOBICITY AND BUBBLE ATTACHMENT TO
THE QUARTZ SURFACE IN THE PRESENCE OF HEXYLAMINE
S12
Andrzej W. Trochimczuk, Anna Jakubiak-Marcinkowska, Sylwia 63
Ronka
NEW, POLAR POLYMERIC ADSORBENTS FOR THE IMPROVEMENT
OF PHENOLS SORPTION
9
III. POSTERS
P1
Monika Baczyńska, Marta Kołodziejska, Magdalena Regel- 67
Rosocka, Cezary Kozłowski, Maciej Wiśniewski
COMPARISION OF TRANSPORT OF ZINC AND IRON IONS THROUGH
POLYMER INCLUSION MEMBRANES (PIM) IN SANDWICH TYPE
MODULE AND GLASS PERMEATION CELL
P2
Justyna Ulatowska, Izabela Polowczyk, Anna Bastrzyk, Tomasz 68
Koźlecki, Joanna Franczak and Zygmunt Sadowski
SORPTION OF HEAVY METAL IONS BY FLY ASH: EXPERIMENTAL
AND MODELING STUDIES
P3
Anna Bastrzyk, Izabela Polowczyk, Aleksandra Molenda, 69
Tomasz Koźlecki, Justyna Ulatowska and Zygmunt Sadowski
ADSORPTION OF Cu(II) AND Ni(II) IONS ONTO GREEN TEA LEAVES
P4
Bernadeta Gajda, Radosław Plackowski, Mariusz B. Bogacki
70
FACILITATED TRANSPORT OF METAL IONS THROUGH POLYMER
INCLUSION MEMBRANES CONTAINING 1-ALKYL-1,2,4-TRIAZOLES
AS A CARRIERS
P5
Mariusz B. Bogacki, Piotr Kujawski
71
THEORETICAL STUDIES ON TRI-OCTYLOAMINE (TOA), TRI-nBUTYL PHOSPHATE (TBP) AND 1-DECYL-IMIDAZOLE (IMID10)
USING MOLECULAR DYNAMICS SIMULATIONS
P6
Rozalina Keremedchieva, Ivan Svinyarov, Milen G. Bogdanov 72
IONIC LIQUID-ASSISTED EXTRACTION AS A SAMPLE PREPARATION
TECHNIQUE FOR HPLC DETERMINATION OF BIOLOGICALLY
ACTIVE ALKALOID GALANTAMINE IN LEUCOJUM AESTIVUM L.
(SUMMER SNOWFLAKE)
P7
Marek Bryjak, Anna Siekierka, Jan Kujawski
73
CAPACITIVE DEIONIZATION METHOD FOR EXTRACTION OF
LITHIUM
P8
Ryszard Cierpiszewski, Joanna Dudczak, Tomasz Kalak, 74
Keisuke Ohto
PAPRIKA WASTE AS A BIOSORBENT FOR REMOVING HEAVY
METALS FROM AQUEOUS SOLUTIONS
P9
Ryszard Cierpiszewski, Patrycja Wojciechowska, Hieronim 75
Maciejewski
ADSORPTION OF Cu(II) FROM AQUEOUS SOLUTIONS ON GELATINSILOXANE HYBRID MATERIALS
10
P10
Piotr Cyganowski, Dorota Jermakowicz-Bartkowiak
76
NEW CORE-SHELL TYPE POLYMERIC SUPPORTS BASED ON THE
AMBERLITE XAD-4 ADSORBENT
P11
Dorota Jermakowicz-Bartkowiak, Piotr Cyganowski
77
ECOFRIENDLY LOW-COST NATURAL BIOSORBENTS TOWARDS
RECOVERY OF GOLD
P12
Joanna Czulak, Antonio Guerreiro, Karima Metran, Francesco 78
Canfarotta, Andrzej Trochimczuk, Sergey Piletsky
CROSS-LINKED HORSERADISH PEROXIDASE BY MODIFIED BIOIMPRINTING PROCESS FOR IMMUNOASSAYS
P13
Yavuz Erdem, İrem Çokgez, B. Filiz Şenkal
79
A NEW POLYMERIC SORBENT FOR REMOVAL OF MERCURY IONS
FROM AQUEOUS SOLUTIONS
P14
D. Y. Feklistov, I. M. Kurchatov, N. I. Laguntsov
80
POSSIBLE MECHANISMS OF THE WATER TREATMENT WITH
ALUMINO-SILICIC REAGENT
P15
Bernadeta Gajda, Mariusz B. Bogacki
81
INFLUENCE OF TEMPERATURE ON TRANSPORT OF Ni(II), Co(II),
Cd(II) AND Zn(II) THROUGH POLYMER INCLUSION MEMBRANES
P16
Magdalena Gierszewska, Jadwiga Ostrowska-Czubenko
82
SEPARATION OF WATER/ALCOHOL MIXTURES WITH CHITOSAN
MEMBRANES
P17
Małgorzata Gnus, Gabriela Dudek, Roman Turczyn, Artur Tórz, 83
Krystyna Konieczny
TRANSPORT PROPERTIES OF CHITOSAN AND ALGINIC
MEMBRANES APPLIED FOR PERVAPORATIVE DEHYDRATION OF
ETHANOL
P18
Gabriela Dudek, Małgorzata Gnus, Anna Strzelewicz, Monika, 84
Krasowska, Roman Turczyn, Artur Tórz
PERMEATION OF ETHANOL AND WATER VAPOURS THROUGH
CHITOSAN MEMBRANES WITH FERROFERIC OXIDE PARTICLES
P19
Antonio Guerreiro and Sergey Piletsky
85
AUTOMATED SYNTHESIS OF MOLECULARLY IMPRINTED POLYMER
NANOPARTICLES
P20
Dominik Zdybał, Andrzej K. Milewski, Agata Jakóbik-Kolon
PMMA-BASED SORBENTS FOR ZINC REMOVAL
86
11
P21
A. Jakóbik-Kolon, A. K. Milewski, K. Karoń, J. Bok-Badura
NEW, HYBRID PECTIN-BASED BIOSORBENTS
P22
Dorota Kołodyńska, Alicja Skiba, Zbigniew Hubicki
88
HYDROGELS APPLICATION IN HEAVY METAL COMPLEXES
REMOVAL
P23
Dorota Kołodyńska, Irmina Pańczuk-Figura, Zbigniew Hubicki 89
REMOVAL OF GLDA COMPLEXES WITH HEAVY METALS
ON N-METHYL-D-GLUCAMINE RESIN
P24
Marta Kołodziejska, Cezary Kozłowski, Jolanta Kozłowska
90
TRANSPORT OF GOLD ACROSS POLYMER INCLUSION MEMBRANES
CONTAINING N-(DIETHYLTHIOPHOSPHORYL)-AZA[18]CROWN-6
P25
Marta Kołodziejska, Cezary Kozłowski, Jolanta Kozłowska, 91
Iwona Zawierucha
RESORCINARENES AS ION CARRIERS OF Au(III), Pt(IV), Pd(II) IN
TRANSPORT ACROSS IMMOBILIZED MEMBRANES
P26
Małgorzata Kujawska, Andrzej W. Trochimczuk
92
MOLECULARLY IMPRINTED POLYMERIC ADSORBENT FOR
βBLOCKERS REMOVAL SYNTHESIZED USING FUNCTIONALIZED
MSU-F SILICA AS A SACRIFICIAL TEMPLATE
P27
Ewa Laskowska, Krzysztof Mitko, Marian Turek
93
MINE WATER NANOFILTRATION – SEPARATION OF MONO AND
POLYVALENT IONS
P28
Magdalena Lech, Anna Trusek-Holownia
94
SEPARATION OF WHEY COMPOUNDS IN PRESSURE MEMBRANE
PROCESSES: PROTOCOL FOR THE ORGANIC COMPOUNDS
FRACTIONATION TO THEIR FURTHER USE
P29
Magdalena Legan, Andrzej W. Trochimczuk
95
FUNCTIONALIZED POLY(HIPE) AS A MONOLITH ADSORBENT FOR
ION EXCHANGE PROCESS
P30
C. M. Mirea, I. Diaconu, E. A. Serban, E. Ruse, G. Nechifor 96
COMPETITIVE TRANSPORT OF Fe(III) AND Mn(II) IONS THROUGH
BULK LIQUID MEMBRANES
P31
Hironori Murakami, Syouhei Nishihama, Kazuharu Yoshizuka
97
SELECTIVE RECOVERY OF Dy FROM WASTE Nd MAGNET USING
COATED SOLVENT IMPREGNATED RESIN
P32
Anna Nowik-Zając, Cezary Kozłowski, Andrzej Trochimczuk
98
SELECTIVE TRANSPORT OF Ag(I) AND Cu(II) ACROSS PLASTICIZED
MEMBRANES WITH CALIX[4]PYRROLES
12
87
P33
Cristina Orbeci, Cristina Modrogan, Alexandra Raluca Miron, 99
Firas Hashim Kamar
REMOVAL OF HEAVY METAL IONS THROUGH ION EXCHANGE
P34
Daniela-E. Pascu, Alexandra R. Miron, Mihaela Pascu (Neagu),
100
Aurelia C. Nechifor, Bogdan I. Bita, Marian C. Popescu,
Cornel Trisca-Rusu, Eugenia Eftimie Totu
STRUCTURAL AND FUNCTIONAL CHARACTERIZATION OF
MEMBRANE PROCESSES, THROUGH SPECIFIC TECHNIQUES AND
MATHEMATICAL MODELS
P35
Mihaela Pascu (Neagu), Daniela-E. Pascu, Andreea Cozea,
Gina A. Traistaru, Alexandra R. Miron, Andrei A. Bunaciu,
Cristina A. Nechifor
COMPOSITE
MEMBRANES
FOR
THE
PROCESSING
BIOLOGICALLY ACTIVE EXTRACTS
101
OF
P36
Beata Podkościelna
102
SYNTHESIS AND PHYSICO-CHEMICAL PROPERTIES OF GMA
TERPOLYMERS FOR ENZYMES IMMOBILIZATION
P37
Beata Podkościelna, Andrzej Bartnicki, Barbara Gawdzik 103
SYNTHESIS, STRUCTURE AND PROPERTIES OF THE NEW
MICROSPHERES WITH LIGNIN UNITS
P38
Izabela Polowczyk, Anna Bastrzyk, Tomasz Koźlecki
104
HYDROPHOBIC AGGREGATION OF FINE CALCIUM CARBONATE
PARTICLES IN AQUEOUS SOLUTION
P39
Justyna Ulatowska, Izabela Polowczyk, Tomasz Koźlecki, Anna 105
Bastrzyk, Ewelina Szczałba, and Zygmunt Sadowski
INFLUENCE OF pH ON ARSENIC(III) REMOVAL BY FLY ASH
P40
Beata Pośpiech
106
EVALUATION OF Pd(II) TRANSPORT FROM AQUEOUS CHLORIDE
SOLUTIONS ACROSS POLYMER INCLUSION MEMBRANES WITH
IONIC LIQUIDS
P41
Piotr Gajewski, Marta Przewoźna, Mariusz B. Bogacki 107
FACILITATED TRANSPORT OF SELECTED ORGANIC ACIDS
THROUGH POLYMER INCLUSION MEMBRANES CONTAINING
1-ALKYL-1,2,4 TRIAZOLES AS CARRIERS
P42
Elżbieta Radzymińska-Lenarcik
108
EXAMINATION OF THE FORMATION OF Cd(II) COMPLEXES WITH
1-ALKYLIMIDAZOLE BY THE LIQUID-LIQUID PARTITION METHOD
13
P43
Elżbieta
Radzymińska-Lenarcik,
Małgorzata
Ulewicz 109
APPLICATION OF POLYMER MEMBRANES WITH 1-ALKYL-4METHYLIMIDAZOLE FOR RECOVERY OF ZINC FROM WASTE
P44
Magdalena Regel-Rosocka, Marta Tarnowska, Agnieszka 110
Markiewicz
REMOVAL OF Zn(II), Cu(II), Co(II), Ni(II) FROM CHLORIDE AND
SULFATE SOLUTIONS WITH MIXTURES OF ACIDIC AND BASIC
EXTRACTANTS
P45
Sylwia Ronka, Honorata Juskiewicz
111
FIXED-BED ADSORPTION OF TRIAZINES ON SPECIFIC POLYMERIC
SORBENT
P46
Fatih Bildik, Bahire Filiz Senkal, Tuba Şişmanoğlu, Erdem Yavuz 112
PREPARATION OF POLY (2-ACRYLAMIDO-2-METHYLPROPANE
SULFONIC ACID) (AMPS) GRAFTED ONTO CROSSLINKED
POLY(VINYLBENZYL CHLORIDE) RESIN FOR REMOVAL OF
ATRAZINE FROM WATER
P47
A. Yu. Smirnov, G. A. Sulaberidze, V. D. Borisevich, S. Zeng, D. 113
Jiang
TRANSIENT PROCESSES IN MODEL CASCADES
P48
Weronika Sofińska-Chmiel, Dorota Kołodyńska
114
PUROLITE S 940 AND PURLITE S 950 IN HEAVY METAL IONS
REMOVAL FROM ACIDIC STREAMS
P49
Weronika Sofińska-Chmiel, Dorota Kołodyńska, Ewaryst 115
Mendyk and Zbigniew Hubicki
REMOVAL OF Cu(II) USING ION EXCHANGE RESINS WITH
ANIONOPHOSHONIC FUNCTIONAL GROUPS
P50
Katarzyna Staszak, Karolina Wieszczyka, Magdalena Regel- 116
Rosocka, Aleksandra Wojciechowska, M. Teresa A. Reis, M.
Rosinda C. Ismael, M. Lurdes F. Gameiro, Jorge M.R. Carvalho
APPLICATION OF PSEUDO-EMULSION BASED HOLLOW FIBER
STRIP DISPERSION (PEHFSD) FOR RECOVERY OF Zn(II)
P51
V. D. Borisevich, A. Yu. Smirnov, G. A. Sulaberidze
117
ON THE SEPARATIVE POTENTIAL (VALUE FUNCTION) FOR
SEPARATION OF MULTICOMPONENT MIXTURES: STATUS OF THE
PROBLEM
P52
Piotr Szczepański, Grażyna Szczepańska
118
THE RESPONSE SURFACE ANALYSIS FOR ESTIMATION OF THE
MASS TRANSFER COEFFICIENT IN PERTRACTION
14
P53
Piotr Szczepański, Romuald Wódzki
119
TRANSPORT AND SEPARATION OF PHENOL AND p-NITROPHENOL
IN AN AGITATED BULK LIQUID MEMBRANE SYSTEM.
EXPERIMENTAL AND THEORETICAL STUDY BY NETWORK
ANALYSIS
P54
Gulcin Torunoglu Turan, B. Filiz Senkal
120
MODIFICATION OF POLY(GLYCIDYL METHACRYLATE) GRAFTED
ONTO
CROSSLINKED
POLY(3-CHLORO-2-HYDROXYPROPYL
METHACRYLATE-METHYL METHACRYLATE (MMA)-ETHYLENE
GLYCOLE DIMETHACRYLATE (EGDMA)) WITH AMINO-BIS-(CISPROPAN 2,3 DIOL) FUNCTIONS FOR REMOVAL OF BORON FROM
WATER
P55
Yuki Ueda, Shintaro Morisada, Hidetaka Kawakita, Keisuke 121
Ohto
SOLVENT EXTRACTION OF PRECIOUS METAL IONS WITH
TRIMETHYLACETAMIDE TYPE OF TRIDENT MOLECULE
P56
Toshiyuki Umebayashi, Syouhei Nishihama, Kazuharu 122
Yoshizuka
OXIDATIVE ADSORPTION OF ARSENIC WITH N-METHYL
GLUCAMINE BASED ADSORBENT AND MANGANESE DIOXIDE
P57
Lavinia Lupa, Adriana Popa, Raluca Voda, Petru Negrea, 123
Mihaela Ciopec, Adina Negrea
STRONTIUM ADSORPTION ON IONIC LIQUID IMPREGNATED
FLORISIL. FIXED-BED COLUMN STUDIES
P58
Raluca Vodă, Lavinia Lupa, Adina Negrea, Mihaela Ciopec, Petru 124
Negrea, Corneliu M. Davidescu
THE DEVELOPMENT OF A NEW EFFICIENT ADSORBENT FOR THE
REMOVAL OF METHYLENE BLUE
P59
Katarzyna Witt, Elżbieta Radzymińska-Lenarcik, Włodzimierz 125
Urbaniak
APPLICATION OF β-DIKETONES DERIVATIVES FOR SELECTIVE
SEPARATION OF COPPER IONS IN THE TRANSPORT PROCESS
ACROSS A POLYMERIC INCLUSION MEMBRANE
P60
Grzegorz Wójcik, Zbigniew Hubicki
126
INVESTIGATION OF CHROMIUM (III AND VI) IONS SORPTION ON
WEAKLY BASIC ANION EXCHANGER
P61
Grzegorz Wójcik, Zbigniew Hubicki, Magdalena Górska
127
NEW SOLVENT IMPREGNATED RESIN AMBERLITE XAD 7 HP FOR
RECOVERY OF GOLD(III) IONS FROM METALLIC SECONDARY
SOURCES
15
P62
Joanna Wolska, Marek Bryjak
128
THERMORESPONSIVE MOLECULARLY IMPRINTED POLYMER FOR
FAST SORPTION AND DESORPTION OF DIETHYL PHTHALATE
P63
REMOVAL OF DIETHYL PHTHALATE
MOLECULARLY IMPRINTED POLYMERS
P64
Gulcemal Yildiz, Filiz Senkal, Nevin Oztekin, Yuksel Orgun
130
THE PROPERTIES OF POLYVINYLIMIDAZOLE-CLAY COMPOSITES
AND THEIR USE FOR REMOVAL OF REMAZOL BLACK FROM WATER
P65
Iwona Zawierucha, Cezary Kozłowski, Jolanta Kozłowska
131
SELECTIVE REMOVAL OF GOLD FROM WASTE RINSE WATER
USING
N-(DIETHYLTHIOPHOSPHORYL)-AZA[18]CROWN-6
IMPREGNATED AMBERLITE XAD-4 RESIN
NOTES
AUTHORS INDEX
16
BY
pH-RESPONSIVE
129
132
142
I. LECTURES
NEW PROSPECTS FOR ADVANCEMENT OF COPPER
HYDROMETALLURGY FOR THE TREATMENT OF HIGH GRADE
COPPER ORES AND CONCENTRATES
David Dreisinger
University of British Columbia, Materials Engineering,
309-6350 Stores Road, Vancouver, Canada V4K4K2
e-mail: david.dreisinger@ubc.ca
The treatment of high grade copper ores and concentrates by
hydrometallurgical methods has largely focused on the application of leach,
solvent extraction and electrowinning technology in the sulphate system. A
simplified process flowsheet showing the outline of the typical process is shown
below.
Copper Ore or Concentrate
Reagents
Wash
Water
Raffinate
Copper Leaching
S/L Separation
Copper SX-EW
Precious Metal
Recovery
Final
Residue
Gold and Silver
Bleed
Copper Cathode
Fig. 1. Generic flowsheet for copper recovery from high grade ores and concentrates
The key aspects of any process are effective copper extraction and recovery as
cathode, by-product gold and silver recovery and production of a stable final
residue for disposal. The recycling of acid, reagents and water and the provision
for a bleed stream are necessary additional features of the flowsheet.
Copper recovery from chalcopyrite ores or concentrates is especially difficult
due to the passivation of chalcopyrite under mild leaching conditions. The
passivation phenomena has one or more causes, depending on the leaching
method and conditions but may be overcome by a variety of methods. These
include:
•
•
•
•
Leach at potential/pH that avoids passivation in the presence of a
galvanic catalyst (eg. Pyrite)
Add silver salts to catalyze copper leaching
Fine grind to P80 of less than 10 μm
Use high temperature (+200°C) aggressive conditions
19
•
•
•
Use chloride or chloride addition
Use bacteria (thermophiles) that avoid passivation
Add oxidation catalyst like nitrate or nitrite (NSC)
These techniques of avoiding passivation have resulted in a range of potential
processes for treatment of chalcopyrite containing materials. These are
summarized in Table 1 below. Included for reference are the Cobre Las Cruces,
Mount Gordon and Sepon Copper Processes which focus on chalcocite ore
treatment but include many of the same elements of leaching technology.
Table 1. Survey of Modern Copper Leaching Technologies (Status: D=demo, P=pilot,
C=commercial)
D
P
P/C
Temp.
(°C)
110
85
150
P
35
1
Yes
No
No
C
C
C
80
150
90
1
12
1
No
No
No
No
Yes
No
No
Yes
No
Dynatec
P
150
12
No
No
Yes
Galvanox
Mt. Gordon
PLATSOL
P
C
P
Sepon Copper
C
Total Press. Ox.
C
80
90
225
80 – Cu
220 – FeS2
225
1
8
32
1
32
32
No
No
No
No
No
No
No
No
Yes
No
No
No
No
No
No
No
No
No
Process
Activox Process
Albion Process
AAC- UBC
Bactech/Mintek
Low T Bioleach
BIOCOP™
CESL Process
Cobre Las Cruces
Status
Press. Ultrafine Chloride Surfactant
Special
(atm) Grind
Considerations
12
Yes
No
No
1
Yes
No
No
12
Yes
No
Yes
Thermo-philes
Chalcocite
Coal+
Recycle
Galvanic
Chalcocite
Chalcocite
This historical operations that have commercially processed copper using these
technologies is shown below.
• Mt. Gordon, Australia – 50,000 tpa Cu (Closed in 2003)
• PD/Freeport Bagdad USA – 16,000 tpa Cu (Converted to MoS2
treatment)
• Alliance Copper, Chile (BIOCOP™) – 20,000 tpa Cu (Closed after 2 year
demo plant operation)
• Sepon Copper, Laos – 90,000 tpa Cu (Continuing to operate)
• Kansanshi, Zambia - +50,000 tpa Cu (Continuing to operate)
• PD/Freeport Morenci USA – 75,000 tpa Cu (Closed)
• Cobre Las Cruces, Spain – 72,000 tpa Cu (Continuing to operate)
• CESL Process, Vale Brazil - 10,000 tpa Cu (Closed after demo plant
operation)
Many copper ores and concentrates contain significant amounts of gold and
silver. The recovery of these precious metals is essential to the economic
treatment of the ores and concentrates. Unfortunately the presence of reactive
iron precipitates, unreacted sulphides, copper minerals and element sulphur
often make the recovery of precious metals challenging or uneconomic. The
20
range of options currently under consideration for treating copper leach
residues for precious metal recovery include the following:
•
•
•
Direct cyanidation
• Complicated by presence of copper and/or elemental sulphur
• Silver may require a lime boil prior to cyanidation to decompose
silver jarosites (if formed during leaching)
Alternative reagent systems including S2O32-, SCN- or Cl-/BrCo-leaching of gold, silver and PGM elements with copper (and other
base metals) using the PLATSOL™ process
Many challenges remain to broaden the application of hydrometallurgy for high
grade copper ores or concentrates. However, the range of possible process
options, the advances taking place in precious metal recovery and the
economic drivers for innovation point to a promising future.
21
NEW HIGHLIGHTS ON URANIUM RECOVERY FROM
PHOSPHORIC ACID: FROM FUNDAMENTAL SCIENCE TO
PROCESS
A. Chagnes1, A. Dartiguelongue1,2, D. Beltrami1, E. Provost2, W. Furst2, G.
Cote1
1 PSL
Research University, Chimie ParisTech - CNRS, Institut de Recherche de
Chimie Paris, 75005, Paris, France,
2 UCP/ENSTA Paristech
e-mail: alexandre.chagnes@chimie-paristech.fr
Wet Phosphoric Acid (WPA), whose concentration is typically ranging between
4 and 6 mol.L-1, is a strategic source of uranium that can be exploited in spite of
the low uranium content (0.1-0.4 g.L-1) and its strong complexing power.
Numerous studies concerned the development of synergic mixtures of
extractants for the recovery of uranium(VI) from wet phosphoric acid but most of
the extractants are not sufficiently selective towards iron. The design of an
efficient and selective extraction system relies on the comprehension of the
chemistry involved during solvent extraction, i.e. the processes occurring in the
aqueous phase, in the organic phase and at the liquid-liquid interface.
For this aim, it is crucial to have (i) a good description of the speciation in
concentrated phosphoric acid as well as in the extraction solvent, (ii) to take into
account the non-ideality in concentrated phosphoric acid and (iii) to have a good
idea of the extraction equilibria involved at the liquid-liquid interface.
This paper focuses on the investigation of the speciation of uranium(VI) in
concentrated phosphoric acid and in the extraction solvent containing a mixture
of bis-(2-ethyl-hexyl)-phosphoric acid (D2EHPA) and tri-n-octylphosphine
(TOPO) in kerosene, as well as the development of a thermodynamic model
based on the Equation of States for modeling the variation of the distribution
ratio of uranium(VI) as a function of the composition of the organic phase and
phosphoric acid concentration between 1 and 7 mol.L -1. From this study
combined with an investigation of the relationship between the chemical
structure of the extracting agents and their extraction properties, few molecules
and a flow sheet have been designed to recover efficiently and selectively
uranium(VI) from WPA.
22
VOLATILE FATTY ACID RECOVERY FROM FERMENTATION
BROTHS
E. Reyhanitash, S. R. A. Kersten, B. Schuur
University of Twente, Sustainable Process Technology group, Meander Building
221, PO box 217, 7500AE Enschede, The Netherlands
e-mail: B.schuur@utwente.nl
Production of bio-based volatile fatty acids is gaining interest. E.g. bio-based
acetic acid has been utilized in bio-plastic production (1) and bio-energy (2). A
recent research direction in our group is aiming at value-added chemical
producing waste management (3), i.e. production of volatile fatty acids (VFAs)
through waste water fermentation. Here presented are studies on the recovery
of these VFAs from model solutions mimicking these broths.
First, a short overview is given on the recent developments in organic acid
recovery, typically reported in literature for ideal aqueous acid solutions. Then
the possible strategies are discussed, including liquid-liquid based recovery and
adsorption based recovery.
For liquid-liquid extraction, the performance of several of the most promising
solvents with artificial fermented wastewater broths is discussed, including the
effect of various salts on the extraction. Since typically concentrations are low,
there is a need to enhance the extraction yield in a sustainable way (thus not by
producing large amounts of salts), and the possibility to apply pressurized
carbon dioxide is discussed.
If the concentrations of the acids are low enough, which is for fermented
wastewaters typically the case (< 10 g / L), next to liquid-liquid extraction also
adsorption may be interesting. Some possible adsorbents are discussed and
results of adsorption studies on VFA adsorption from artificial solutions
mimicking fermented wastewater are presented.
In both liquid-liquid extraction and adsorption, not only the primary recovery
from the broth is of importance, but also the regeneration of the separating
agent. The comparison of both approaches includes regeneration strategies
and an outlook on how affinity separation may be applied in a continuous
process.
References:
1. C. Mengmeng et al., Bioresour. Technol., 100 (2009) 1399-1405.
2. B. Uyar, I. Eroglu, M. Yücel and U. Gündüz, I. J. Hydrogen Energy, 34 (2009) 4517-4523.
3. W. S. Lee, A.S. M. Chua, H.K. Yeoh, G.C. Ngoh, Chem. Eng. J., 235 (2014) 83-99.
23
DOWNSTREAM PROCESS – HOW TO CAPTURE A PROTEIN?
Dorota Antos
Rzeszów University of Technology, Faculty of Chemistry,
Department of Chemical and Process Engineering,
Powstańców Warszawy 6 Ave., 35-959 Rzeszów, Poland
e-mail: dorota.antos@prz.edu.pl
Recently, the demand for purified proteins such as: specific antibodies, protein
conjugates, recombinant proteins, virus like particles etc., has increased
considerably for medical use as well as for advanced diagnostics. The world
market of biopharmaceuticals and recombinant proteins reached nearly 140 bln
USD in 2014. The share in the market is illustrated in Fig. 1.
Antibodies
Fig. 1. Share of the market according to La Merie Publishing www.lamerie.com
Because of the complexity of mixtures obtained as a product of fermentation
processes, to obtain a target product with a desired purity a high number of
purification stages is required, which involves high energy and chemical
consumption (Fig. 2).
As purification process has become a crucial part of biotechnology, high interest
has been aroused in cost-effective techniques that can separate proteins and
be easily adopted for large scale operations. Various separation techniques
have been developed including: extraction, precipitation, crystallization,
membrane processes, and chromatography. They belong to the most
commonly used methods due to mild operating conditions, which ensure
maintaining the biological activity of the protein.
24
Fig. 2. Flowsheet scheme of production of bioactive proteins
The presentation will introduce the participants to separation techniques used in
downstream processing of proteins. Particularly, chromatographic methods will
be discussed and their coupling with extraction or membrane processes for
efficient isolation of therapeutic proteins. As an example the isolation of a
monoclonal antibody from a cell culture supernatant and a recombinant protein
from inclusion bodies will be shown (1,2).
The monoclonal antibodies constitute an important category of biotechnology
drugs, which are being applied against a number of previously incurable
diseases. Monoclonal antibodies are typically produced in Chinese hamster
ovary (CHO) cell expression systems, where they are secreted from the cells.
Due to the complexity of the supernatant mixtures isolation of the target protein
requires development and design of efficient flowsheet schemes.
The inclusion body (IB) proteins are formed as a result of over-expression of
recombinant proteins in Escherichia coli, where they occur in high
concentrations. Moreover, because they can be washed with differential
centrifugation, they are obtained in a rather pure form. However, they take a
partially-folded, inactive form, which needs to be renatured to recover biological
activity, and purified. Also in this case the efficient combination of different
purification techniques is of the major importance (3,4).
References:
1. W. Marek et al., J. Chromatogr. A, 1305 (2013) 55-63.
2. W. Marek et al., J. Chromatogr. A, 1305 (2013) 64-75.
3. S. Ryś et al., Eng. Life Sci., 15 (2015) 140-151.
4. S. Ryś et al., Chem. Eng. Sci., 130 (2015) 290-300.
25
MOLECULARLY IMPRINTED POLYMER NANOPARTICLES
PREPARED BY THE SOLID-PHASE APPROACH: PLASTIC
ANTIBODIES FOR SEPARATIONS, ASSAYS AND SENSORS
Michael J. Whitcombe, Sergey A. Piletsky, Elena V. Piletska, Antonio
Guerreiro, Kal Karim
Leicester Biotechnology Group, Department of Chemistry, College of Science
and Engineering, University of Leicester, George Porter Building, University
Road, Leicester, LE1 7RH, UK
e-mail: mw319@le.ac.uk
Molecularly Imprinted Polymers (MIPs) are a generic solution to the challenge
of preparing robust materials with the property of molecular recognition.
Recognition sites are created in the material by the formation of a cross-linked
matrix entrapping the molecule of interest (the template) by its association with
functional monomers. Binding sites are therefore created by a self-assembly
process. Removal of the template is then required in order for the sites to be
used. Traditional methods of MIP synthesis produce materials that fall short of
the ideal encapsulated in this description. The commercial application of these
materials is so far limited to a few applications in solid phase extraction and
sensing. A far greater potential could be realised if the materials could directly
replace antibodies in existing applications and technologies. We recently
developed a new method for the synthesis of soluble molecularly imprinted
polymer nanoparticles (nanoMIPs) using a solid-phase approach (1,2) which
allows us to do exactly that. We will show that the materials prepared in this
way are physically stable, high affinity antibody analogues that can compete
with antibodies in separations, assays, sensors and biological targeting.
NanoMIPs have on average one binding site per particle and the methods of
synthesis allows for the incorporation of diverse additional functionalities (e.g.
fluorescent dyes, electroactive labels, PEG etc.) during their preparation (3).
NanoMIPs are therefore deserving of the name “plastic antibodies”.
References
1. S. Piletsky et al., WO2013041861, 28 March 2013.
2. A. Poma et al., Adv. Funct. Mater., 23 (2013) 2821-2827.
3. E. Moczko et al., Nanoscale, 5 (2013) 3733-3741.
26
ROLE OF POLYMERIC MATERIALS IN SEPARATION SCIENCE
Barbara Gawdzik
Department of Polymer Chemistry, Maria Curie Skłodowska University,
Gliniana 33, 20-614 Lublin, Poland
e-mail: barbara.gawdzik@poczta.umcs.lublin.pl
This lecture will focus attention upon studies under polymeric porous materials
used in separation science, mainly in HPLC, GC and SPE techniques.
In 1954 Sober and Peterson made the observation that proteins could be
adsorbed by diethylaminoethyl derivatized cellulose and then subsequently
eluted by the eluent of an increasing ionic strength. This example of the use of a
polymeric anion exchanger for liquid chromatography was followed by the use
of a carboxymethyl cellulose derivative for cation exchange chromatography
and a cross-linked polydextran gel which in the swollen state was used for size
separation of water-soluble biological macromolecules. It is interesting to note
that the first modern liquid chromatograph utilized polymeric packing materials.
This instrument developed by Moore and Stein worked as an amino acid
analyzer. Its glass column contained irregular particles of sulfonated
polystyrene-divinylbenzene.
At our Department of Polymer Chemistry MCS University, we are concerning on
the synthesis of new porous, highly crosslinked polymeric materials mainly in
the shape of microspheres. The progress in the preparation of polymeric
microspheres in different sizes and particle size distributions by special
polymerization techniques will be presented. The incorporation of chemical
functional groups into microspheres will be discussed in two ways: the first one
concerning the synthesis of new functional (meth)acrylate monomers
subsequently used in the preparation of microspheres, and the second one
regarding chemical modification of primary polymeric microbeads. The
evaluation of the chromatographic properties of polymeric packings and their
application in separation and determination of some pesticides, amines and
drugs will be presented.
A special attention will be paid on the inverse GC and reversed phase HPLC
studies which allow determining packings’ selectivity and polarity. As an
example of polymeric microparticles application in ion chromatography, organic
dendrimeric materials will be shown.
In the course of the lecture the synthesis and application of some molecularly
imprinted polymers will be also mentioned.
Apart from porous polymers, the polymer – based carbon materials and their
usage in separation science will be presented as well. Moreover, preparation of
the crosslinked polymers based on lignin and their application in SPE will be
given.
27
II. SHORT LECTURES
NEW EXTRACTANTS FOR THE RECOVERY OF COBALT AND
NICKEL ACIDIC CHLORIDE SOLUTIONS
K. Omelchuk1, M. Haddad2, G. Cote1, A. Chagnes1
1 PSL
Research University, Chimie ParisTech - CNRS, Institut de Recherche de
Chimie Paris, 75005, Paris, France
e-mail: kateryna.omelchuk@chimie-paristech.fr
Cobalt and nickel are strategic metals from many applications including alloys
manufacturing, electrode materials for lithium-ion batteries (LIBs), etc. Their
recovery from spent materials is a good opportunity from economical and
geopolitical viewpoints as these metals are expensive and recycling reduces
considerably supply risks of cobalt and nickel, particularly in the forthcoming
years during which cobalt and nickel demands will likely increase significantly
with the emergence of electric vehicles. Therefore, recovery of cobalt and nickel
from LIBs is strategic and development of efficient and economic processes is
coming to the fore.
Several research activities were carried out to recycle strategic metals from
spent batteries by different methods such as pyrometallurgy, hydrometallurgy
and biohydrometallurgy. Pyrometallurgical processes are however energy
intensive and release gases like sulfur dioxide and carbon dioxide which are
harmful to the environment. In recent past, metallurgical industry has been
searching for hydrometallurgical processes due to some advantages such as
possibility of treating low-grade resources, easier control of wastes and lower
energy consumption. Hydrometallurgical processes are based on physical
separation, leaching, purification, precipitation and in some cases electrowining.
The demand for high purity metals and recent trends towards environmentally
friendly technology has focused more attention onto solvent extraction because
this technology is mature and permits to achieve high extraction efficiency at
low operating costs.
Cyanex 272 is a dialkyl phosphinic acid extractant widely used for the
separation of cobalt from nickel to obtain high purity cobalt salts that can be
reused to produce high-grade products for lithium-ion batteries. However,
extraction occurs at pH close to 4 for cobalt and 6 for nickel and addition of
alkaline solutions to adjust the pH is required. In order to decrease operating
expenditure, the use of extracting agents capable to recover and separate
cobalt, nickel, lithium and manganese at lower pH and in few stages is
mandatory.
The aim of this work is to study the influence of the chemical structure of
various organophosphorus compounds synthesized at the laboratory scale on
the extraction efficiency of cobalt and nickel vs. pH. In particular, the influence
of branching, hydrophobicity and the presence of oxygen atoms in alkyl chains
has been investigated for several organophosphorus compounds such as
bis(1,3-dibutoxypropan-2-yl) phosphoric acid, bis(1,3-diisobutoxypropan-2-yl)
phosphoric acid, bis(5,8,12,15-tetraoxanonadecan-10-yl) phosphoric acid and
bis(undecan-6-yl) phosphoric acid.
31
LANTHANUM REMOVAL FROM AQUEOUS SOLUTIONS USING
FLORISIL IMPREGNATED WITH TETRABUTYLAMMONIUM
DIHYDROGEN PHOSPHATE
Andreea Gabor1, Corneliu Mircea Davidescu1, Adina Negrea1, Mihaela
Ciopec1, Petru Negrea1, Cătălin Ianași2
1 Politehnica
University Timişoara, Faculty of Industrial Chemistry and
Environmental Engineering, Victoriei Square Nr. 2, 300006 Timişoara, România
2 Institute of Chemistry Timişoara of Romanian Academy, Romanian Academy,
Blv. Mihai Viteazul no. 24, 300223 Timişoara, România
e-mail: emeline_gabor@yahoo.com
CANCELLED
1. Introduction
Lanthanum makes part of a group of 17 chemically similar metallic elements
named rare earth elements (REEs). This group contains the 15 lanthanides plus
scandium and yttrium (1) and is further divided in light rare earth elements
(lanthanum, cerium, praseodymium, neodymium, promethium, and samarium)
and heavy rare earth elements containing the rest of lanthanides elements with
yttrium (2). These elements can be found in the earth crust with many reserves
in about 34 countries (3). They can be naturally found mixed and scattered in
minerals, which makes their separation from each other difficult because of the
very similar physico-chemical properties (2). REEs are used in many industries
due to their metallurgical, optical and electronic properties, but also in
agriculture (3). REEs have been used in China as fertilizers in low
concentrations for a long period of time. Consequently, it led to a bioaccumulation in the environment (4).
Lanthanum represents about 30% of the total amount of REEs used. China is
the largest consumer of lanthanum and lanthanides using them in
manufacturing electronic products. Lanthanum is used in petroleum refining,
automobile catalytic converters. It is also added to glass and alloys to improve
specific properties. Lanthanum is used in applications that require the
production of coloured light. In large amounts lanthanum is used in
rechargeable nickel-metal-hydride batteries to store hydrogen (5). So far many
methods have been tried out for separation or preconcentration of REEs
including La(III): liquid-liquid extraction (6,7), coprecipitation (8), ion-exchange
(9), solid phase extraction (10-12), biosorption (13), cloud point extraction (14),
dispersive liquid-liquid microextraction (15-18), solidified floating organic drop
microextraction (19).
This study aims to the removal of lanthanum through adsorption on
functionalised material with nitrogen and phosphorus groups. The
functionalisation of the used material had as purpose the improving of its
sorbent properties. Kinetic studies have been carried out in order to determine
the conditions of the adsorbent process of lanthanum. The novelty of this study
is the use as extractant quaternary ammonium salts which have nitrogen and
phosphorus groups, unused till know in literature. Concomitantly in this study,
magnesium silicate is used as solid support which in literature is less used for
32
functionalisation with the mentioned salts as extractant. Most of the studies
focus on silica as inorganic support (20,21).
2. Materials and methods
The functionalisation of the solid support was made using the dry method. For
improving the sorbent properties of the solid support (magnesium silicate)
nitrogen and phosphorus groups from quaternary ammonium salts
(tetrabutylammonium dihydrogen phosphate - TBAH2P) were used for
functionalisation. To highlight the nitrogen and phosphorus groups, the obtained
material was characterized through different physico-chemical methods: energy
dispersive X-ray analysis (EDX), scanning electron microscopy (SEM) using a
Scanning Electron Microscopy Quanta FEG 250, equipped with Energy
Dispersive X-ray quantifier (EDAX ZAF), FTIR analysis using a Shimadzu
Prestige- 21 FTIR spectrophotometer in the range 4000–400 cm-1 and BET
surface area analysis using a Nova 1200 E Quanta Chrom.
CANCELLED
3. Results and discussion
3.1. Characterisation of the functionalised material
Figures 1-3 point out the presence of the nitrogen and phosphorus groups on
the solid support as a result of the functionalisation of the material through
impregnation. This was realised using physico-chemical characterisation
methods on the functionalised material.
Figure 1 shows the FTIR spectrum of the solid support, extractant, adsorbent
material after impregnation with tetrabutylammonium dihydrogen phosphate
(TBAH2P) and after using it in the removal process by adsorption on column of
La(III).
Fig. 1. FTIR spectrum of Florisil, TBAH2P, impregnated adsorbent material and
impregnated adsorbent material with La(III)
The Florisil spectrum shows a strong band at 1080 cm -1 which can be attributed
to the Si-O bond (22). The TBAH2P presents an overlapping of the adsorption
bands characteristic for C-N bonds between 1250-1020 cm-1 (23) and for P-O
bonds between 1250-1210 cm-1 (24). Also the peaks at 1460 cm-1 and 1380 cm1 are corresponding to the C-H deformation vibrations (24). The spectrum of the
impregnated adsorbent material presents an overlapping of the adsorption
bands for all specific bonds that can define it: Si-O, C-N, P-O in the region of
1200-950 cm-1. After using the adsorbent material in the sorption-desorption
cycles, an additional peak appeared at 3400 cm -1, that can be assigned to the
O-H bond from La(OH)3 (25).
33
Figure 2 presents the surface morphology of Florisil after impregnation. The
SEM image after impregnation reveals white spots that confirm the presence of
the TBAH2P extractant used for impregnation. Also, the EDX spectrum (Figure
3) shows the presence of specific atoms like C, P, N of the extractant.
(a)
(b)
Fig. 2. Surface morphology of the adsorbent material (a) before impregnation and (b)
after impregnation
CANCELLED
Fig. 3. The EDX spectrum of the impregnated adsorbent material
From the BET study it can be observed a decrease of the specific surface of the
material after impregnation, which indicates a modification inside the pores,
confirming that the impregnation took place.
3.2. La(III) adsorption studies
In order to study the adsorption process of La(III) on Florisil impregnated with
TBAH2P, the influence of different parameters (solid : liquid ratio, time contact,
initial concentration and temperature) on the adsorption capacity of the material
were determined.
Kinetic studies were also carried out. It was studied the influence of the contact
time on the adsorption capacity. The data were fitted with the pseudo-first order
and the pseudo-second-order kinetic models to establish the kinetic model of
the adsorption process of La(III) on the impregnated material. The equilibrium
nature of the adsorption of La(III) onto the impregnated material was describe
using the Langmuir and Freundlich isotherm models. It has been found that the
adsorption process of La(III) fits to the Langmuir isotherm model.
4. Conclusions
The study shows that the impregnation of Florisil with tetrabutylammonium
dihydrogen phosphate took place and leads to a higher adsorption capacity in
34
the removal process of La(III) from aqueous solutions. From the kinetic studies
the best fit of the experimental data had the pseudo-second-order model. This
is given by the high correlation coefficient and the small difference between the
experimental and calculated adsorption capacity.
By comparing the data of the equilibrium studies, the Langmuir model
represents better adsorption process of La(III) onto Florisil impregnated with
TBAH2P. The correlation coefficient for the Langmuir model is bigger than for
the Freundlich model and the difference between the experimentally obtained
adsorption capacity 8.95 mg/g and the calculated capacity 9.06 mg/g is
negligible 0.1 mg/g. The adsorption of La(III) onto Florisil impregnated with
tetrabutylammonium dihydrogen phosphate (TBAH2P) is characterized by a
homogenous adsorption on the surface of the material and the sites are
energetically equivalent without effecting the adsorption on adjacent sites.
CANCELLED
References
1. K. Binnemans et al., J. Clean. Prod., 51 (2013) 1-22.
2. J. Ponou et al., J. Environ. Chem. Eng., 2 (2014) 1070-1081.
3. S. Unal Yesiller et al., J. Ind. Eng. Chem., 19 (2013) 898-907.
4. L. Wang et al., Chemosphere, 103 (2014) 148-155.
5. R.P. Wedeen, B. Berlinger, J. Aaseth, in “Handbook on the Toxicology of Metals:
Lanthanum”, Eds. G.F. Nordberg, B.A. Fowler, M. Nordberg; Academic Press, 4 edition,
2014, 903-909.
6. M.B. Shabani et al., Anal. Chem., 62 (1990) 2709-2714.
7. S. Radhika et al., Sep. Purif. Technol., 75 (2010) 295-302.
8. T.J. Shaw et al., Anal. Chem., 75 (2003) 3396-3403.
9. P. Moller et al., Spectrochim. Acta, Part B, 47 (1992) 1379-1387.
10. S.A. Kumar et al., Desalination, 281 (2011) 49-54.
11. C. Karadaș et al., Water Sci. Technol., 69 (2014) 312-319.
12. R. Kala et al., Anal. Chim. Acta, 518 (2004) 143-150.
13. Y. Andrès et al., Environ. Technol., 24 (2003) 1367-1375.
14. Y. Li et al., J. Hazard. Mater., 174 (2010) 534-540.
15. K. Chandrasekaran et al., J. Anal. At. Spectrom., 27 (2012) 1024-1031.
16. M.H. Mallah et al., Environ. Sci. Technol., 43 (2009) 1947-1951.
17. M.H. Mallah et al., J. Radioanal. Nucl. Chem., 278 (2008) 97-102.
18. İ. Çelik et al., Talanta, 134 (2015) 476-481.
19. S. Chen et al., Microchim. Acta, 180 (2013) 1479-1486.
20. D. Caldarola et al., Appl. Surf. Sci., 288 (2014) 373-380.
21. A. Zhang et al., Eur. Polym. J., 44 (2008) 3899-3907.
22. P.J. Launer, in “Infrared analysis on organosilicon compounds: spectra-structure
correlations”, Eds. B. Arkles et al., Petrarch Systems, 1987.
23. F. An et al., React. Funct. Polym., 73 (2013) 60-65.
24. K.K. Yadav et al., Sep. Purif. Technol., 143 (2015) 115-124.
25. M. Salavati-Niasari et al., J. Alloys Compd., 509 (2011) 4098-4103.
35
PRECIOUS METAL RECOVERY FROM THE WASTES
USING ION EXCHANGE METHOD
Kazuharu Yoshizuka, Shuhei Tanaka, Hironori Murakami,
Syouhei Nishihama
Department of Chemical Engineering, The University of Kitakyushu,
Hibikino 1-1, Kitakyushu 808-0135, Japan
e-mail: yoshizuka@kitakyu-u.ac.jp
1. Introduction
Precious metals such as Au, Pd, Pt, and Rh are included in the wastes of
electronic appliances and automobiles. Although demand for precious metals is
still increasing in recent years, the primary supply of PGMs is restricted to the
mines located in a few limited countries. Separation and recovery of the
precious metals from wastes called “urban mine” is nowadays an active issue
(1). The present separation and recover process of the metals is based on the
solvent extraction. However, solvent extraction is high environmental load,
because it requires large amount of organic solvent. Alternative separation
process being more environmentally friendly is expected instead of solvent
extraction.
In the present study, the selective recovery of precious metals from LED and
automobile catalyst is investigated using ion exchange method. For the
recovery of Au from aqua regia leachate of LED, weak base anion exchange
resin (DIAION WA-21J) was used. For the recovery of Pd, Pt, and Rh from
concentrated HCl leachate of automobile catalyst, solvent impregnated resin
and WA-21J were used. The chromatographic operation of the metals was
performed to achieve the precious metal recovery.
2. Recovery of Au from Waste LED
The waste LED terminal was first taken off from the lamp. The LED terminal
was then treated with aqua regia ([aqua regia] = 12.0 mol/L) in an autoclave at
80°C for 24 h. The resultant suspension was then filtered, and the metal
concentrations were determined by ICP-AES. Table 1 shows the compositions
leached from the waste LED.
Table 1. Leaching amount of metals
Element
Fe
Ca
Ag
Au
Leaching amount (mg/g)
12.8 6.77 > 1.96 2.17
Mn
0.0584
Zn
0.596
Adsorption behavior of Au and co-existed metals in the leaching solution with
WA21J was investigated in batchwise system. Figure 1 shows the time course
variation of the adsorption yield of the co-existed metals in the actual leaching
solution after 10-times dilution ([aqua regia] = 1.2 mol/L). Adsorption of gold
was reached to equilibrium within 9 h. Adsorption yields of the co-existed metals
except for the gold were quite low.
Chromatographic separation of Au with WA21J was then investigated. Figure 2
shows the breakthrough and elution curves of Au from actual leachate (1.2
36
mol/L aqua regia). Before the breakthrough of Au, 21.1 mg of Au was adsorbed,
and quantitative elution could be achieved by 0.1 mol/L thiourea solution.
100
2000
(a)
Au
Fe
Ca
Ag
Mn
Zn
50
[ Au ] ( mg/L )
Adsorption yield ( % )
10
0
0
5
10
15
20
(b)
5
1000
0
25
0
0
200
400
600
Time ( h )
800
0
50
100
Bed Volume ( - )
Fig. 1. Time course variation of
adsorption yield of Au, Fe, Ca, Ag,
Mn, and Zn with WA21J
Fig. 2. (a) Breakthrough curve and (b) elution
curve of Au from actual leaching solution
3. Recovery of Pd, Pt and Rh from waste automobile catalyst
Dihexyl sulfide (DHS) impregnated resin was used for adsorbent of Pd and WA21 was used for the adsorbent of Pt and Rh. Chromatographic separation of Pd,
Pt and Rh are conducted by using DHS impregnated resin and WA-21. Figure 3
shows the elution curves of the metals from DHS impregnated resin. Pd can be
selectively eluted with the elution yield of 98 %. On the other hand, DHS
impregnated resin has no adsorption ability of Pt and Rh by chromatographic
operation. Figure 4 shows the elution curves of the metals from WA-21 column.
The elution of Pd and Pt progresses simultaneously, while Rh can be selectively
eluted by changing the eluent. The results indicate the possibility of mutual
separation of Pd, Pt and Rh by the combination of DHS impregnated resin and
WA-21.
H2SO4
Thiourea / HCl
1000
30000
(b) Elution
(b) Elution
Rh
Pd
Pt
20000
800
[ PGMs ] [ mg/L ]
[ PGMs ] [ mg/L ]
25000
15000
10000
Rh
Pd
Pt
600
400
200
5000
0
0
0
2
4
6
8
B. V. [ - ]
Fig. 3 Elution curves of Pd, Pt and Rh
from DHS impregnated resin; Eluent: 0.1
mol/L thiourea - 1 mol/L HCl
0
20
40
60
80
100
120
B. V. [ - ]
Fig. 4 Elution curves of Pd, Pt and Rh from
WA-21; Eluents: 0.1 mol/L thiourea / 1
mol/L HCl and 1 mol/L H2SO4
Acknowledgements: We are grateful for the financial support through The Research and
Technology Development Fund from the Ministry of Environments of Japan.
References
1. S. Nakamura, N. Kojima, K. Yokoyama, J. MMIJ, 123 (2007) 799-802.
37
SEPARATION OF NICKEL(II) AND CADMIUM(II) IONS WITH IONEXCHANGE AND MEMBRANE PROCESSES
Jerzy Gęga, Paulina Otrembska
Częstochowa University of Technology, Department of Chemistry,
19 Armii Krajowej Str., 42-200 Częstochowa, Poland
e-mail: gega@wip.pcz.pl
Separation of nickel(II) and cadmium(II) ions with use of ion-exchange resins –
Amberlyst 15 and Lewatit OC 1026, supported liquid membranes (SLM),
polymer inclusion membranes (PIM) and ion-exchange membranes (IM) from
sulphate solution has been studied. Di-2-ethylhexylphosphoric acid (D2EHPA)
was used as the ion-carrier in PIM and SLM separation processes. It was
shown that use of SLM or PIM membranes enables separation of Ni(II) and
Cd(II) ions. Experimental results data show that the highest recovery factor
values were obtained for supported liquid membranes.
1. Introduction
Nickel and cadmium are used on mass scale in many branches of industry. Use
of different products that contain these metals creates a problem with their
utilization. Methods, which could be used for removal and recovery of Ni(II) and
Cd(II) ions from water and wastewater are: precipitation (1), membrane
transport (2-4), ion-exchange (5-7) or liquid-liquid extraction (7).
In this paper, the separation of Ni(II) and Cd(II) ions from sulphate solutions with
use of SLM and PIM membranes with D2EHPA as a carrier, IM with Amberlyst
15 and ion-exchange processes with Amberlyst 15 and Lewatit OC 1026 has
been studied. There are two part of the study: firstly the study of separation with
use of resins and secondary comparison obtained data with results from
membrane transport.
2. Experimental
Solution of known metals ions concentrations was prepared by dissolving an
appropriate salt: nickel(II) sulphate hexahydrate and cadmium(II) sulphate 8/3hydrate in deionized water. The pH was adjusted by the addition of appropriate
volume of sulphuric acid or sodium hydroxide solutions.
The resins used were: Lewatit OC 1026 (Lanxess) and Amberlyst 15 (Rohm &
Haas). Lewatit OC 1026 is a resin based on crosslinked polystyrene matrix with
adsorbed di-2-ethylhexylphosphate (D2EHPA) and Amberlyst 15 is a resin
containing sulfonic acid groups. The sorption of nickel(II) and cadmium(II) onto
resins was carried out by means of the batch method. The appropriate volume
of metal salt solution and resin were contacted for certain time (30 or 60
minutes). Concentrations of metal ions were measured by atomic absorption
spectrometry (SOLAAR 939) with an air/acetylene flame and the suitable hollow
cathode lamps. All experiments were carried out at room temperature.
As a support in SLM experiments a PTFE-filter (Whatman) with a pore size of
0.2 µm and diameter 47 mm were used. These filters were soaked in 1 M
38
D2EHPA solution in kerosene. To synthesize of polymer inclusion membranes,
solutions of cellulose triacetate, the ion carrier (D2EHPA) and the plasticizer
(orto-nitrophenyl octyl ether, ONPOE) in dichloromethane were prepared. The
CTA, ONPOE and D2EHPA solutions were mixed and a portion of this solution
was poured onto a Petri dish. The organic solvent was allowed to evaporate
overnight. Afterwards the membrane was separated from glass by immersion in
distilled water and was conditioned in 0.1 M HCl for 12 hours. To synthesize of
ion-exchange membranes solutions of poly(vinyl chloride), ONPOE and grinding
resin in tetrahydrofuran were mixed and similarly as PIM poured onto a Petri
dish. After evaporate of organic solvent membrane was conditioned in 0.5 M
NaCl (48 hours) and then in 0.1 M HCl (12 hours)
Transport experiments were carried out during 24 hours in a permeation cell in
which the membrane was tightly clamped between two cell compartments one
with a donor phase (0.01 M solution of metal salts, pH=3 for PIM and SLM or
pH=1 for IM) and second with an acceptor solution (0.5 M H2SO4).
Effect of agitation time on nickel(II) and cadmium(II) sorption on Amberlyst 15
which is strongly acidic cation (SAC) exchange resin and Lewatit OC 1026 –
chelating resin has been studied. Fig. 1 demonstrates that the amount of the
adsorbed metal ions onto investigated exchange resins increases with time.
The sorption of Ni(II) and Cd(II) was rapid for the first 5 min. and equilibrium
was reached after 20 min. Therefore, the period of 30 min. was considered as
the optimum time for all ion-exchange experiments presented in the paper.
1.0
1.0
Ni(II)
Cd(II)
0.8
0.8
0.6
c/c0
c/c0
0.6
0.4
0.2
(a)
0.4
0.2
0.0
0
10
20
30
t, min
40
50
60
(b)
Ni(II)
Cd(II)
0.0
0
10
20
30
40
50
60
t, min
Fig. 1. Effect of agitation time of Ni(II) and Cd(II) sorption in ion-exchange processes
with: (a) Amberlyst 15 and (b) Lewatit OC 1026 resin. Initial concentration of metal
ions: 10 mM, pH=0 (Amberlyst 15) or pH=3 (Lewatit OC 1026), resin/solution ratio: 1:10
The pH of initial solution is a very important factor, which influenced sorption
process and recovery of investigated metal ions. Concentration of H+ ions
controls the surface charge of the adsorbent and ionization of the adsorbate in
solution. The influence of pH on the sorption of nickel(II) and cadmium(II) from
sulphate solution was investigated in the range of 0 to 5 and is shown in Fig. 2.
The results indicate that the lowest c/c0 value was obtained for resin with
sulfonic groups (Amberlyst 15). It was found that for separation of Ni(II) and
39
Cd(II) ions on Amberlyst 15 initial solution of pH=1 should be used. In the case
of ion-exchange processes with Lewatit OC 1026 pH=3 would be effective.
1,0
1,0
Ni(II)
0,8
0,8
0,6
Metal ions init. conc.:
0,1 M
0,01 M
0,001 M
0,0001 M
0,4
0,2
c/c0
c/c0
0,6
0,2
Cd(II)
0,8
0,8
0,6
c/c0
0,6
c/c0
Ni(II)
0,0
1,0
0,0
1,0
(a)
Metal ions init. conc.:
0,1 M
0,01 M
0,001 M
0,0001 M
0,4
0,4
0,4
0,2
0,2
0,0
0,0
0
1
2
3
pH
4
5
(b)
Cd(II)
0
1
2
3
4
5
pH
Fig. 2. Effect of initial concentration and pH of Ni(II) and Cd(II) ions on the sorption
effectiveness. Ion exchangers: (a) Amberlyst 15, (b) Lewatit OC 1026. Initial
concentration of metal ions: 0.0001 M – 0.1 M, pH = 0 – 5, resin/solution ratio: 1:10,
process time: 30 min
Ion exchange is an equilibrium reaction that is also dependent on the ionic
concentrations of various ions both inside and outside of resin bead. Effect of
initial concentration of Ni(II) and Cd(II) ions in aqueous solution on their sorption
have been also studied. The results are presented in Fig. 2. The amount of
adsorbed metal ions is dependent on the initial metal ion concentration. The
calculated values of sorption capacity (SC) show that better results are obtained
for Amberlyst 15 (1.36 mval/g) than for Lewatit OC 1026 (0.23 mval/g).
Fig. 3 demonstrates 24 hours membrane transport with use of supported liquid
membrane, polymer inclusion membrane and ion-exchange membrane. Di-2ethylhexylphosphoric acid (D2EHPA) was used as the ion-carrier in PIM and
SLM separation. In contrast to IM membranes, which provided low c/c0 value
and separation of nickel(II) and cadmium(II) ions was very low also, it was
shown that use of SLM or PIM membranes enables separation of Ni(II) and
Cd(II) ions. It was suggested that Ni(II) ions stay in donor phase when PIM or
SLM membranes were used.
40
1.0
0.8
0.8
0.6
0.6
c/c0
c/c0
1.0
0.4
Ni(II)
Cd(II)
0.2
(a)
0.0
5
Ni(II)
Cd(II)
0.2
(b)
0
0.4
10
15
20
25
0.0
0
5
10
t, h
15
20
25
t, h
1.0
0.8
c/c0
0.6
0.4
0.2
(c) 0.0
Ni(II)
Cd(II)
0
5
10
15
20
25
t, h
Fig. 3. The influence of time on nickel(II) and cadmium(II) concentrations in feed
solutions in membranes experiments: (a) SLM or (b) PIM (0.05 g CTA, 0.208 g ONPOE
and 2 M D2EHPA (on volume of plasticizer)), (c) IM (0.4 g PVC, 1 g Amberlyst 15,
0.208 g ONPOE). Transport conditions are described in section: Experimental
3. Conclusions
The obtained experimental results of nickel(II) and cadmium(II) ions separation
with use of method like ion-exchange process or transport through membranes
prove the possibility of application of this processes to selective separation of
these metals from sulphate solution. Better separation was obtained for
membrane processes. The minimum c/c0 value of Cd(II) was received in 24 h
for SLM membranes, higher for IM and PIM membranes. It was suggested that
Ni(II) ions stay in donor phase when PIM or SLM membranes were used.
References
1. K. Provazi et al., Waste Management, 31 (2011) 59-64.
2. R. Mahmoodi, et al., Chemical Papers, 68 (2014) 751-756.
3. J. Gega, P. Otrembska, Sep. Sci. Technol., 49 (2014) 1756-1760.
4. B. Gajda, M. Bogacki, J. Achiev. in Mater. Man. Eng., 55 (2012) 673-678.
5. S K. Pang, K.C. Yung, Ind. Eng. Chem. Res., 52 (2013) 2418-2424.
6. P. Otrembska, J. Gega, Physicochem. Probl. Miner. Process., 49 (2013) 301-312.
7. J.M. Kumar et al., Hydrometallurgy, 111–112 (2012) 1-9.
41
REACTIVE EXTRACTION AS A METHOD FOR REMOVAL
OF LOW MOLECULAR CARBOXYLIC ACIDS
FROM FERMENTATION BROTH
Magdalena Regel-Rosocka, Agnieszka Krzyżkowska, Maciej Wiśniewski
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
This work is a part of a project investigating biotechnological conversion of
glycerol to polyols and dicarboxylic acids. The paper focused on separation of
such carboxylic acids as formic, acetic, succinic, lactic and butyric, from model
and real fermentation solutions using reactive extraction with solvating
extractant Cyanex 923. 0.1 or 0.4 M solutions of Cyanex 923 in the organic
phase were used to investigate influence of aqueous/organic phase ratio (w/o)
on extraction of acids and selectivity of acid separation from glycerol or
propane-1,3-diol. The results showed that carboxylic acids could be separated
from polyols in multistage extraction with 0.4 M Cyanex 923.
Introduction
According to idea of sustainable development, industry is looking for new
sources of raw materials - secondary sources that can be recovered,
regenerated and/or reused. In the light of such attitude, bioprocesses are
becoming an important way to process various effluents and wastewater to
produce valuable chemicals. The results presented in this work are a part of a
project investigating biotechnological conversion of glycerol to polyols and
dicarboxylic acids. Separation of particular components of the fermentation
broth is a crucial stage of technological process affecting its successful
application. There are reported various methods for recovery of fermentation
broth components, among them membrane techniques, adsorption,
crystallization, reactive extraction (1-3).
The paper focuses on separation of such carboxylic acids as lactic, formic,
acetic, succinic from glycerol and propane-1,3-diol from model solutions using
reactive extraction with Cyanex 923 solutions.
Experimental
Extraction was carried out in a typical way: various volume ratios of the
aqueous feed and the organic phase (w/o) were shaken for 15-60 minutes at
20°C in glass separatory funnels and then allowed to stand for phase
separation. For the next step of extraction fresh organic phase was contacted
with the raffinate from the previous stage. 0.1 or 0.4 M Cyanex 923 (trialkyl
phosphine oxides - solvating extractant) solutions in Exxsol D 220/230 were
used as the organic phase.
Composition of the fermentation broth as declared by its producer the Poznan
University of Life Sciences is presented in Table 1.
42
Table 1. Declared composition of the fermentation broth
Component
Content declared, g/dm3
Propane-1,3-diol (PD)
32
Real broth, g/dm3
30
Lactic acid (Lac)
3.5
3.0
Acetic acid (Ac)
3.1
1.9
Butyric acid (But)
3.5
3.8
Formic acid (For)
0.98
0.9
Glycerol (Gl)
0.44
below 0.1
Succinic acid (Suc)
0.31
below 0.1
pH = 8.3
Compositions of model solution originated from the real fermentation broth
composition are also presented in Table 1. Two-component model solutions
contained always succinic acid and glycerol, propane-1,3-diol or one of other
acids. Determination of broth components was carried out with HPLC
chromatography with refractometric detector and silica HYDRO-RP column (C18
groups).
Results and discussion
Previously obtained results and literature data (4) indicate that dicarboxylic
acids (H2A) and solvating extractants (S) react according to the following
equation: H2 A  nS  (H2 A  Sn ) . Succinic acid extracted with Cyanex 923 is
likely to form 1:2 or 2:3 acid:extractant complexes (5).
The opportunity to separate succinic acid from model fermentation broth
containing based on the composition declared in Table 1 was investigated. Only
butyric acid was not included in the model solution. To concentrate the acids in
the organic phase a o/w=1/2 ratio was applied. Composition of raffinates after
extraction with 0.1 or 0.4 M Cyanex 923 is presented in Fig. 1.
3.5
0.1 M Cyanex 923
0.4 M Cyanex 923
before extraction
3.5
2.5
3.0
2.0
3
3
2.5
co, g/dm
caq, g/dm
0.1 M Cyanex 923
0.4 M Cyanex 923
3.0
30
2.0
1.5
1.0
1.5
1.0
0.5
0.5
0.0
For
Ac
Lac
Suc
Component
a)
Gl
PD
0.0
For
Ac
Lac
Suc
Gl
PD
Component
b)
Fig. 1. Composition of a) raffinates and b) extracts after extraction with () 0.1 or ()
0.4 M Cyanex 923 from model solution (- -- -)
As it is seen in Fig. 1, the carboxylic acids were partly extracted from the model
feed. The raffinate after extraction with 0.4 M Cyanex 923 contained mainly
acetic acid, less formic and finally less than half of the initial content of succinic
43
acid. When the lower concentration of extractant was used the order of
extraction was the following: Lac < Suc < For < Ac.
The real fermentation broth was acidified to pHi=2.3 prior to three stage
extraction to convert all acid salts into their acidic forms. The concentration of
succinic acid declared by the producer of the broth (Table 1) was actually much
smaller, and it could not be determined. Therefore, succinic acid was not
present in the research on the real broth.
Table 2. Distribution ratio of the real broth components in three stages of extraction
(o/w=1/2)
Distribution ratio, D
But
3.73
2.78
55.1
0.1 M Cyanex 923
0.4 M Cyanex 923
For
Ac
Lac
But
For
Ac
Lac
I stage of extraction
0.48
0.39
0.16
20.1
2.74
1.28
0.46
II stage of extraction
0.35
0.25
0.18
4.36
2.64
0.85
III stage of extraction
0.81
0.65
0.17
4.29
2.29
0.77
Efficiency of acid extraction from real fermentation broth decreased in the
following order (Table 2): butyric >> formic ~ acetic > lactic acids. Butyric acid is
completely removed from the broth in the first stage of extraction with more
concentrated Cyanex 923 (0.4 M).
Studies on extraction from the fermentation broth indicated that the system is
not selective for extraction of low molecular carboxylic acids but almost
completely selective for polyols. Therefore, it is possible to separate the acids
from polyols. The possibility for recovery of the carboxylic acids from the real
solution – the broth after glycerol fermentation to propane-1,3-diol – was
assessed.
60
two-component solution
model broth
real broth
0.1 M Cyanex 923
0.4 M Cyanex 923
50
%E
40
30
20
10
0
For
Lac
Ac
Component
Fig. 2. Comparison of extraction of the carboxylic acids from two-component (),
model () and real broth solutions () with 0.1 (- - -) or 0.4 M ( ̶ ) Cyanex 923
44
Comparison of extraction of the carboxylic acids from various solutions, i.e. twocomponent (succinic - formic; succinic - lactic or succinic - acetic), model
solution and the real broth is presented in Fig. 2.
The extraction efficiency of the acids increases, irrespective of the solution type,
in the following order: Lac < Ac < For. The lowest values of acid extraction are
obtained from the real broth, then the model broth and the highest from twocomponent model solution. The real fermentation broth contains a lot of various
components including e.g. proteins or butyric acid that can affect negatively
extraction of the other carboxylic acids. Butyric acid was not included in the
model solutions because of its bothersome odour.
Conclusions
Carboxylic acids can be separated from the broth in multistage extraction.
Extraction of acids is selective regarding polyols. Propane-1,3-diol and glycerol
are strongly hydrated due to many hydroxyl groups present in the molecules
and their affinity to the hydrophobic organic phase is rather low. Thus,
extraction with Cyanex 923 can be used to separate polyols from carboxylic
acids that are prone (particularly butyric and formic) to react with the organic
phase.
Acknowledgements: This research was supported by the project „Biotechnological conversion of
glycerol to polyols and dicarboxylic acids” implemented within the Operational Programme –
Innovative Economy, 2007- 2013, co-financed by the European Union grant POIG.01.01.02-00074/09)
References
1. Y.K. Hong et al., Biotechnol. Bioprocess Eng., 6 (2001) 386-394.
2. T. Kurzrock, D. Weuster-Botz, Biotechnol. Lett., 32 (2010) 31-339.
3. K. Prochaska et al., Bioresour. Technol., 167 (2014) 219-225.
4. M. Pierzchalska, M. Wiśniewski, Proceedings of the XXth International Symphosium on
Physico-Chemical Methods of the Mixture Separation, “ARS SEPARATORIA 2005”, (2005)
96-100.
5. A.S. Kertes, C.J. King, Biotechnol. Bioeng., 103 (2009) 432-445.
45
IONIC LIQUIDS AS ALTERNATIVE SOLVENTS FOR SELECTIVE
EXTRACTION OF SECONDARY METABOLITES FROM PLANT
MATERIALS: A CASE STUDY
Milen G. Bogdanov, Rozalina Keremedchieva, Ivan Svinyarov
Faculty of Chemistry and Pharmacy, University of Sofia St. Kl. Ohridski,
1, James Bourchier Blvd., 1164 Sofia, Bulgaria
e-mail: mbogdanov@chem.uni-sofia.bg
In continuation of a research project aiming at introducing ionic liquids (ILs) as
an alternative to the widely applied for the recovery of natural products of
industrial interest conventional molecular solvents (1-3), we developed a
concise procedure for isolation of the biologically active alkaloid S-(+)-glaucine
from IL-based aqueous crude extract. To this end, a comparative study of the
behavior of 1M [C4C1im][Ace]-aqueous solution and methanol in a series of
consecutive extractions with the same extractant was conducted. The results
obtained proved the better performance of the IL-based system in the solid–
liquid extraction step, since the latter showed constantly higher extraction
efficiency (ca. 35% enhanced) compared to methanol. The above procedure
allows glaucine accumulation from at least ten successive extractions, while
simultaneously reduces the total solid–liquid ratio from 1:40 to 1:7.2, without
loss of efficiency. Furthermore, the loss of IL into the matrix pores after
extraction was also considered, suggesting the need for IL recycling by posttreatment of the residual biomass. To recover glaucine from the crude IL-based
aqueous extract, a series of non-miscible with water molecular solvents were
tested. As a result, optimal conditions for quantitative extraction into chloroform
were found, from which, after solvent removal and subsequent crystallization
from ethanol, the target compound was isolated as a hydrobromide salt, the
latter being the marketed form of glaucine.
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. Bogdanov et al., Sep. Purif. Technol., 97 (2012) 221-227.
2. M. Bogdanov, I. Svinyarov, Sep. Purif. Technol., 103 (2013) 279-288.
3. M. Bogdanov, R. Keremedchieva, I. Svinyarov, Sep. Purif.
doi:10.1016/j.seppur.2015.02.003
46
Technol.,
(2015)
PHOSPHONIUM IONIC LIQUIDS AS METAL ION CARRIERS
THROUGH POLYMER INCLUSION MEMBRANES (PIM) AND
SUPPORTED LIQUID MEMBRANES (SLM)
M. Baczyńska1, M. Regel-Rosocka1, T. M. Coll2, A. Fortuny2, A. M. Sastre2,
M. Wiśniewski1
1 Poznań
Institute of Technology, Institute of Chemical Technology and
Engineering, Berdychowo St.4, 60-965 Poznań, Poland,
2 Universitat Politêcnica de Catalunya, Department of Chemical Engineering,
Av. Victor Balaguer 1, 08800 Vilanova i la Geltru, Spain
e-mail: monika.z.baczynska@doctorate.put.poznan.pl
Introduction
Many researchers proposed application of supported liquid membranes and
polymer inclusion membranes as an alternative method to traditional liquidliquid extraction (SX). The advantages of these membranes over SX include
elimination in amount of volatile solvents from separation systems and reduction
of intermediate steps (1). Phosphonium ionic liquids are frequently proposed to
be used for separation of metal ions both in adsorption and extraction systems.
In recent years many workers proposed application of these compounds as
SLM and PIM carriers for metal ions such as Cd(II), Zn(II) and Fe(III) from
chloride aqueous solutions (2-4).
In this work, the authors present results of investigation on transport of Zn(II),
Fe(II), Fe(III) across SLMs and PIMs containing phosphonium ionic liquids as
metal ion carriers.
Experimental
Reagents and solutions
The inorganic chemicals, i.e., Zn(II), Fe(II) and Fe(III) chlorides were of
analytical grade. The organic reagents, i.e., cellulose triacetate (CTA), onitrophenyl ether (NPOE), dichloromethane, decanol, kerosene were also of
analytical grade and were purchased from Fluka and used without further
purification. Phosphonium ionic liquids, i.e. trihexyltetradecylphosphonium
chloride (Cyphos IL 101) and trihexyltetradecylphosphonium bis(2,4,4trimethylpentyl)phosphinate (Cyphos IL 104) supplied by Cytec Industry Inc.
(USA) were applied as carriers for metal ions in PIMs. The aqueous feed phase
containing 1.5∙10-3 M (Zn) and 1.8∙10-3 M Fe (0.1 g/dm3), 0.58 M HCl, 5 M Cl(NaCl was used to obtain constant chloride content). 1 M H 2SO4 was used as
receiving phase.
Supported and Polymer Inclusion Membranes - preparation
To prepare the PIMs a solution of cellulose triacetate as the polymer matrix,
plasticizer (NPOE), Cyphos IL 101 and Cyphos IL 104 as ion carriers in
dichloromethane was prepared. A specific portion of the solution was poured
into a Petri dishes. After slow organic solvent evaporation the obtained polymer
inclusion membrane was carefully peeled off from the glass dish by immersion
in a cold water. A porous membrane of polytetrafluoroethylene film (Durapore
HVHP04700, pore size 0.45 µm, porosity 75%, thickness 125 µm) was used as
47
polymeric support. The organic liquid membrane phase was prepared by
dissolving the required volume of Cyphos IL 101 and Cyphos IL 104 in 10%
decanol/kerosene to obtain carrier solutions. The supported liquid membranes
were prepared at room temperature by impregnating the porous film with the
carrier solution overnight, then leaving them to drip for 10 s before being placed
in apparatus.
Transport studies
To transport Zn(II), Fe(II) and Fe(II) across PIMs, a sandwich type membrane
module was used, to which feed and receiving phase were pumped with a
peristaltic pump from tanks containing both phases. The volumes of aqueous
solutions were equal 200 cm3. The effective membrane area was 15.9 cm2.
The SLM transport experiment was carried out in the flat sheet (FSSLM)
apparatus. Batch experiments were carried out in two cylindrical cells containing
210 cm3 of feed and receiving solutions. The effective area of SLM was equal to
11.4 cm2. Both phases were mechanically stirred. Samples from the feed and
receiving phases were withdrawn at regular time intervals, and metal ion
concentration was analysing by atomic absorption spectroscopy (AAS, Hitachi
Z-8200 and Shimadzu UV-1603) at 218 and 248.3 nm (respectively for zinc and
iron) in the air-acetylene flame.
The kinetics of membrane transport can be described by a first order reaction in
metal ion concentration:
ln
c
 kt
c0
(1)
where co (M) and c (M) are the concentrations of metal ions in the feed phase at
initial time and selected time, respectively, k is the rate constant (s-1), t is the
time of transport (s). Values of the rate constant (k) are estimated from linear
dependence of ln(c/co) versus time.
Transport abilities of PIMs and SLMs are characterized by the following
parameters:
- Initial flux (Jo, mol/m2∙s)
J0 
V
 k  c0
A
(2)
where V is the volume of both aqueous phases, A is the effective membrane
area,
- Permeability coefficient (P, m/s)
P
V
k
A
(3)
Results and discussion
Figure 1 shows the mass transport of Zn(II), Fe(II) and Fe(III) ions across SLM
and PIM.
48
a)
b)
Fig. 1. Initial flux (a) and permeability coefficient (b) of Zn(II) (■), Fe(II) ( ) and Fe(III)
(□) ions across SLM and PIM
As shown in Fig.1a the best results of initial flux are obtained for Zn(II) across
SLM membranes containing Cyphos IL 101 (J0 equal 21∙10-6, mol/s∙m2), in the
case of Zn(II) transport through PIM containing the same carrier the value of
initial flux is equal to 14∙10-6, mol/s∙m2. Almost no transport of Zn(II), Fe(II) and
Fe(III) is noted with SLM containing Cyphos IL 104 (very low values of J 0). The
similar tendency is observed for values of permeability coefficient (1b).
Transport abilities of PIMs and SLMs can be characterized by extraction
efficiency (E, %) and recovery factor (RF, %) of metal ions (calculated after 48
or 72 h of process, for Zn(II) and Fe ions, respectively) and are defined by the
following equations:
E
c0  c
100%
c0
(4)
cs
100%
c0
(5)
RF 
cs is the concentration of Fe ions in the receiving phase at the selected time.
The values of percentage extraction (a) and recovery factor (b) of SLMs and
PIMs of Zn(II), Fe(II) and Fe(III) are illustrated in Fig. 2.
Comparing the values of extraction efficiency and recovery factor we can see
that the best results are obtained for Zn(II) across PIMs (the values of E and RF
at least 80%). Also Fe(III) is successfully transported across PIMs and SLMs.
The lowest transport efficiency is noticed for Fe(II) extraction.
49
a)
b)
Fig. 2. The comparison of the values of (a) extraction efficiency and (b) recovery
factors of Zn(II) (■), Fe(II)( ) and Fe(III) (□) through SLMs and PIMs containing
Cyphos IL 101 and Cyphos IL 104
Conclusions
Transport of Fe(II) and Fe(III) through PIMs is faster than transport across SLM.
On the other hand transport of Zn(II) is faster across SLM. For SLM and PIM
containing Cyphos IL 101 as ion carrier over 80% of initial amount of Zn(II) and
Fe(III) was extracted, while in the case of Fe(II) this value was less than 40%.
Cyphos IL 104 extracted Zn(II) and Fe(III) as good as IL 101 only with PIMs. In
the case of SLM, this carrier transferred efficiently only Fe(III).
Generally, the transport of the metal ions through both types of membranes is
comparable and indicates that both phosphonium ionic liquids are mobile
carriers to transfer Zn(II) and Fe(III) from the feed to the receiving phase. The
difference between SLM and PIM lies in initial flux of metal ions. The initial
transport of the three metal ions is very small, however finally extraction
efficiency and recovery factor are comparable both for PIM and SLM.
Acknowledgments: Monika Baczynska was financially supported within the project “Engineer of
the Future. Improving the didactic potential of the Poznan University of Technology”POKL.04.03.00-00-259/12, implemented within the Human Capital Operational Program, co
financed by the European Union within the European Social Fund.
This work was supported by the 03/32/DS-PB/0501 grant.
References
1. L.D. Nghiem et al., J. Membr. Sci., 281 (2006) 7-41.
2. J. Castillo et al., Hydrometallurgy, 141 (2014) 89-96.
3. D. Kogelnig et al., Monatsch. Chem., 142 (2011) 769-772.
4. M. Regel-Rosocka et al., Sep. Purif. Technol., 97 (2012) 158-163.
50
INFLUENCE OF COMPOSITION OF MEMBRANE ON
TRANSPORT OF SELECTED ORGANIC ACIDS THROUGH
POLYMER INCLUSION MEMBRANE
Marta Przewoźna, Piotr Gajewski, Mariusz B. Bogacki
Poznań University of Technology, Institute of Chemical Technology and
Engineering, Berdychowo 4, 60-965 Poznań, Poland
e-mail: marta.przewozna@doctorate.put.poznan.pl
1. Introduction
Special kind of liquid membranes are polymer inclusion membranes (PIM).
They are thin, flexible but stable membranes, composed of polymer matrix,
carrier and plasticizer. The amount of compound used as a carrier in
preparation of polymer inclusion membranes is significantly smaller than in the
extraction process (1-3). Additionally, polymer inclusion membranes are more
stable in comparison with other liquid membranes. In the case of supported
liquid membrane (SLM), organic phase is suspended in the pores of the
microporous membrane, while in PIM, organic phase fills the entire volume of
the membrane. During preparation of polymer inclusion membrane, solution of
polymer matrix is directly mixed with solution of carrier and after evaporation of
solvent, membrane is produced. Thanks to that, carrier is built in the structure of
the polymer matrix and during transport no carrier elution from the polymer
matrix is observed.
Polymer inclusion membrane should be uniform and transparent, respectively
flexible, durable and resistant to mechanical stress such as tensile, bending and
other deformations. Very important factor is the compatibility between used
polymer matrix and a carrier. In some cases it is necessary to use a plasticizer
in order to improve the mechanical properties or improve the compatibility
between polymer matrix and a carrier. However some compounds used in the
preparation of polymer inclusion membranes can play both a plasticizer and a
carrier function. Therefore, important is appropriate selection of qualitative and
quantitative composition of the membrane for selective separation of
substances from their solution (2,3). Accordingly, the aim of conducted
researches is to provide PIMs characterized by a high flux and selectivity of
transported substances. Therefore, very useful could be analysis of influence of
polymer inclusion membrane composition on transport rate.
2. Experimental
Transport of organic acids through polymer inclusion membrane was carried out
using two glass chambers. One chamber contained feeding phase while second
chamber contained receiving phase. The volume of each phase was 45 cm3.
During the separation process each phase was intensively stirred. Between the
chambers a polymer inclusion membrane was placed. The surface of the
membrane was equal to 4.15 cm2. Scheme of the experimental apparatus is
shown in the Figure 1.
51
Fig. 1. Experimental apparatus diagram: 1−chamber with receiving phase, 2−chamber
with feeding phase, 3−polymer inclusion membrane, 4−stirrers, 5−electrode,
6−temperature sensor
During the study of organic acids transport, as a feeding phase 0.1 M solution of
the appropriate acid was used. As a receiving phase demineralized water was
applied. Separation process was carried out for 24 hours. To determine the
concentration of organic acids, conductivity of receiving phase was measured
every 7 minutes for the duration of the process. Based on the previously
determined calibration curve, the conductivity was converted to the molar
concentration of organic acid in the receiving phase.
For the synthesis of polymer inclusion membranes, cellulose triacetate (CTA),
cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB) and
poly(vinyl chloride) (PVC) as a polymer matrix were used. 1-alkylimidazoles
(Imi-n) and 1-alkoxymethylimidazoles (Oxy-n) were applied as a carrier. The
alkyl chain in 1-alkylimidazole contained 10, 11, 12, 14 or 16 carbon atoms, and
in 1-alkoxymethylimidazole contained 6, 7, 8, 9, 10, 11 or 12 carbon atoms. The
mass fraction of a carrier in the prepared membranes changed from X = 0.027
to X = 0.46.
Based on the basic relationship of transport through polymer inclusion
membranes, the mathematical model describing the transport of organic acid
through polymer inclusion membranes has been proposed:

1 
2C  A
   Pt ,
ln 1 
2 
C 0  V
(1)
where, C0 - the initial concentration of the organic acid [mol/dm 3],
C - concentration of organic acid in the receiving phase at time t [mol/dm 3],
V - volume of feeding/receiving phase [m3], A - surface of membrane [m2],
k - rate constant [1/s], t - time [s], P- permeability coefficient [m/s].
Knowing the rate constant k, the volume of a feed phase and the surface of a
membrane, permeability coefficient can be determined as (P [m/s]):
V
(2)
P  k ,
A
and the flux (J [mol/(m2*s]) can be determined:
V
(3)
J   k  C0 .
A
The studies of oxalic, tartaric and lactic acids transport through polymer
inclusion membranes were conducted. In research, influence of different
52
carriers and their concentration, as well as the type of used polymer matrix were
examined. For each of the processes, parameters characterize transport were
determined in accordance with the equations (1-3).
Figure 2 shows an influence of polymer matrix and a carrier kind on transport
rate of organic acids through PIM. In order to compare results of transport, the
membrane thickness was taken into account and J·d parameter was calculated.
As it could be seen (Fig. 2a), in the case of Imi-n, transport rate of organic acids
increases with increasing carbon atoms number in a carrier from 10 to 14.
However, further increase of chain length to 16 carbon atoms causes the
decrease in the transport rate. Whereas, comparing the type of used polymer
matrix, relationship in transport rate PVC > CTA > CAB > CAP is observed. This
series coincide with increasing molecular weight of the polymer matrix. The
highest value was obtained for the matrix with the highest molecular weight.
Whereas, comparing cellulose matrixes, it could be seen that the best
parameters of transport were observed for the membrane with the highest
content of acetyl group.
In the case of Oxy-n used as carriers (Fig. 2b), it could be seen that increase of
carbon atoms number in substituent of a carrier causes increase of transport
rate of tartaric acid. Analyzing the type of polymer matrix used in PIM, it should
be noted that the highest transport values were obtained for the CTA then the
CAB and the lowest for the PVC. Similar dependences were obtained for the
other examined organic acids.
Fig. 2. Influence of polymer matrix and carrier on the transport rate of (a) oxalic acid (b)
tartaric acid by PIM. Polymer matrix: ■CTA, ■CAB, ■CAP, ■PVC. Carrier: (a) Imi-n. (b)
Oxy-n. Temperature 25°C. Feeding phase: 0.1 M solution of organic acid. Receiving
phase: demineralized water
In the next part of this work the study of transport of organic acids: oxalic,
tartaric and lactic acids through polymer inclusion membrane were carried out in
order to determine the effect of qualitative and quantitative composition of the
polymer inclusion membrane on the transport rate of selected organic acids. On
the basis of obtained results and percolation theory, theoretical description of
the phenomenon of separation processes was proposed. Also percolation
threshold for the separated organic acids was determined.
Figure 4 shows the change in the relative concentration of oxalic acid in function
of time of the transport process for various contents of the carrier which is Imi14 using PVC as a polymer matrix. As it can be seen the transport rate of oxalic
53
acid increases with increasing amounts of the Imi-14 in the membrane.
Simultaneously, the time in which equilibrium is achieved is significantly
reduced. A similar situation occurs with other carriers and for the tartaric and
lactic acid.
Fig. 4. Change of the relative
concentration of oxalic acid during
transport through PIM. Polymer matrix:
PVC. Carrier: Imi-14
Fig. 5. Dependence of J·d of oxalic acid
vs.mass fraction of carrier during
transport through PIM. Polymer matrix:
PVC. Carrier: Imi-14
Figure 5 shows the dependence of J·d on the mass fraction of the carrier in the
membrane for Imi-14. It can be seen, that for the content of the carrier below
mass fraction equal X =0.13, no transport of oxalic acid was observed. Above
the minimum carrier content the rapid nonlinear growth of the transport rate until
a maximum value could be seen. A similar situation occurs with other applied
carriers and polymer matrixes as well as for the tartaric and lactic acids.
4. Conclusions
Compounds used in the research as a carriers are compatible with the polymer
matrix in the form of cellulose derivatives and PVC. Compatibility of the carrier
with the polymer matrix results from the presence of free electron pair in its
structure, which facilitates a strong interaction with the chlorine atom in the
poly(vinyl chloride) or the ability of the active compound to a dipole-dipole
interaction, which leads to compatibility with cellulose derivatives. While, the
differences in the transport rate for a variety of polymer matrixes can be related
with their structure and molecular weight.
Additionally, on the basis of the study it can be concluded that the transport of
organic acids through the polymer inclusion membrane based on the
mechanism of jumping (fixe site jumping). Evidence for such transport
mechanism is the presence of percolation threshold and non-linear increasing
of transport rate of organic acids after crossing the critical value.
Acknowledgements: This work was carried out in part the framework of Statutory Research
03/32/DSMK/0519 conducted at the Poznan University of Technology.
References
1. C.V. Gherasim et.al., Dig. J. Nanomater. Bios., 6 (2011) 1499-1508.
2. L. Nghiem et.al., J. Membr. Sci., 281 (2006) 7-41.
3. N. Pereira et.al., Desalination, 236 (2009) 327-333.
54
NANOFILTRATION OF TETRAMETHYLAMMONIUM HYDROXIDE
BY USING MFI-TYPE ZEOLITE COATED MEMBRANE
Syouhei Nishihama, Yasuhiro Tsutsumi, Takeru Mino, Kazuharu Yoshizuka
e-mail: nishihama@kitakyu-u.ac.jp
1. Introduction
Tetramethyl ammonium hydroxide (TMAH) is widely used as a developer for
semiconductor devices and liquid crystal panels and thus is contaminated in the
wastewater discharged from manufacturers. The treatment of waste solutions
containing TMAH has recently become an important issue from an
environmental protection point of view, because TMAH is a toxic organic alkali.
In the present work, separation and recovery of TMAH by nanofiltration using an
MFI-type zeolite (ZSM-5) coated membrane were investigated.
2. Experimental
MFI-type zeolite powder was prepared by hydrothermal synthesis with tetraethyl
orthosilicate, tripropylammonium bromide, sodium hydroxide, and water. MFItype zeolite coated membrane was prepared on an α-alumina support by
hydrothermal synthesis with same reagents.
Adsorption of TMAH with the MFI-type zeolite powder was carried out by
shaking the zeolite powder and TMAH aqueous solution at 25°C for more than
3h. Nanofiltration of the TMAH was carried out by using dead-end mode or
cross-flow mode apparatuses. In the case of the dead-end mode, the
membrane was placed in 100 mL dead-end cell, and then 50 mL of ca. 10 mg/L
TMAH solution (pH = 10) was placed into the upper part of cell. The cell was
then pressurized to permeate 25 mL of the TMAH solution. In the case of the
cross-flow mode, ca. 10 mg/L TMAH solution was fed into the cell at 0.080
MPa, and then both permeate and retentate solutions were collected. The
concentration of the TMAH was measured by an ion chromatograph.
Adsorption property of TMAH with MFI-type zeolite powder was first
investigated. Figure 1 shows the effect of pH on the amount of TMAH adsorbed.
The zeolite possessed a high adsorption capacity for TMAH at all pH range,
because zeta potential of the zeolite is negative at all pH range. The amount
adsorbed slightly increased with pH values < 11, due to slight dissolution of Si.
The MFI-type zeolite-coated membrane was applied to nanofiltration of TMAH
from aqueous solution in the dead-end mode. Figure 2 shows the concentration
profiles of TMAH in the permeate at different pressure. In the case of 0.080
MPa, all TMAH was completely rejected by the membrane and no TMAH was
found in the permeate, while the rejection efficiency of TMAH was decreased in
the cases when the pressure was increased. Because, the concentration of
TMAH in boundary layer is quite increased due to the concentration polarization
induced near the membrane during the nanofiltration operation (1). In the case
55
of nanofiltration with 0.080 MPa, the concentration of the retentate after
0.8
[ TMAH ] ( mg/L )
10
q ( mmol/g )
0.6
0.4
0.2
Feed concentration
MFI-type zeolite coated membrane
(0.080 MPa)
(0.100 MPa)
(0.125 MPa)
5
0
0.0
0
5
10
0
15
10
pH
20
30
V ( mL )
Fig. 1. Effect of equilibrium pH on the
amount of TMAH adsorbed
Fig. 2. Concentration profile of TMAH in
permeate solution with dead-end mode
nanofiltration was 17.8 mg/L, while the feed concentration was 10.2 mg/L.
Based on a material balance, 75% of the TMAH was rejected by the membrane
by the molecular sieve mechanism and 25% possibly adsorbed on or within the
membrane. The nanofiltration of TMAH with the membrane therefore proceeds
under two mechanisms of molecular sieve and adsorption.
10x10-6
5x10-6
0
15
[ TMAH ] ( mg/L )
3
2
J ( m /m s )
The nanofiltration of TMAH with
the MFI-type zeolite coated
membrane with cross-flow mode
was finally investigated. Figure 3
shows concentration profiles of
the TMAH in the permeate and
retentate, together with the
volume flux of the solutions.
TMAH could be perfectly rejected
until ca. 300 min, and then TMAH
was gradually leaked into the
permeate as same as the case
with the dead-end mode. In
addition, the volume flux was
stable during the operation. The
volume flux of the permeate was
however lower than that of the
retentate. The optimization of the
operational condition should be
therefore carried out.
10
Permeate
Retentate
5
0
0
References
1. S.I. Nakao et al., J. Chem. Eng.
Japan, 14 (1981) 32-37.
56
100
200
300
400
500
Time ( min )
Fig. 3. Concentration profile of TMAH and
volume flux with cross-flow mode
MICELLAR-ENHANCED ULTRAFILTRATION FOR REMOVAL OF
METAL IONS FROM AN AQUEOUS SOLUTION
Katarzyna Staszak1, Roksana Drzazga1, Daria Wieczorek2
CANCELLED
(12 pt)
1 Institute of Technology and Chemical Engineering, Poznan University of
Technology, ul. Berdychowo 4, 60-965 Poznań, Poland,
2 Department of Technology and Instrumental Analysis, Faculty of Commodity
Science, Poznań University of Economics, al. Niepodległości 10, 61-875
Poznań, Poland
e-mail: Katarzyna.Staszak@put.poznan.pl
(12 pt,)
Introduction
Traditional methods of elimination or recovery of heavy metals ions from
aqueous solution include precipitation, ion exchange, crystallization,
evaporation, liquid-liquid extraction (1). A promising technique for the
decontamination of wastewater containing these metals is also the micellar
enhanced ultrafiltration (MEUF) (2). Basic idea of this process is that the
surfactant solution, with the concentration higher than the critical micelle
concentration (CMC), is added to the solution containing the separated
compounds. When the surfactant concentration is above the CMC value,
micelles with their hydrodynamic diameter significantly larger than the pore
diameter of the ultrafiltration membrane are formed. Dissolved organic
compounds are usually soluble in the micelles while dissolved ions are usually
adsorbed on the micelles surface due to electrostatic binding on the surface of
the opposite-charged micelles. Micelles containing solubilized/bound
contaminants with diameter larger than the membrane pore size are rejected by
the membrane during the ultrafiltration process, thus only water, unsolubilized
contaminants, and the monomeric form of the surfactant pass through the
membrane. The choice of surfactant is one of the key issues in the ultrafiltration
process. The selection of an appropriate surfactant is important not only to
obtain a high separation efficiency of metal ions, but also to find a
biodegradable compound with low toxicity so that this process could be more
environmentally friendly.
In this work the application of zwitterionic surfactants is proposed. These
surfactants exhibit excellent surface properties. They show low surface tension
and critical micelle concentration. Zwitterionic surfactants are good wetting
agents and can be high, moderate or low foaming surfactants. Probably the
most important class of amphoteric surfactants are amidopropyl betaines, in
particular Cocamidopropyl Betaine (CAPB) (3). It is a popular and widely used
zwitteronic surfactant. CAPB is predominately used as a cosmetic ingredient
and as a detergent (50 % of the produced volume in Europe – 29500 tons/year)
(4). It is commonly used in the cosmetics and household chemicals, i.e.
shampoos, roll-on deodorants, contact lenses solutions, toothpastes, makeup
removers, bath gels, skincare products, cleansers, liquid soaps, the antidandruff products, an exfoliating and peel-off products. Due to the mild nature
and low degree of skin irritation it is also used in cosmetics for children.
Cocamidopropyl Betaine is present with other surfactants (anionic, nonionic) in
57
the commercially available products. The general formula of CAPB is shown in
Fig. 1.
Fig. 1. General formula of Cocamidopropyl Betaine
The aim of this study was to check possibility of using zwitterionic surfactant in
the process of recovery of nickel(II) ions from aqueous solution by micellar
enhanced ultrafiltration.
CANCELLED
Experimental
The sample of Cocamidopropyl Betaine was purchased from one of the
cosmetics company available on polish market (5). It was stored in refrigerator
and not examined, after specified by the producer expiration date. According to
the manufacturer’s information, the commercial CAPB consists of 30%
Cocamidopropyl Betaine and 70% water.
Nickel(II) sulfate hexahydrate (POCh, Poland) was used as a source of nickel
ions in ultrafiltration. Sodium dodecyl sulfate (SDS, Sigma-Aldrich) typical
anionic surfactant was used as the additional surfactant in MEUF process.
The critical micelle concentrations of Cocamidopropyl Betaine were determined
from the surface tension isotherm in a classical way as interception points of the
straight lines just before and after CMC. The surface tension measurement was
made by Du Noüy ring method using tensiometer Krüss K12.
The foaming properties of the aqueous solutions of Cocamidopropyl Betaine
were set in a glass apparatus using the Ross-Miles method in accordance with
the standard ASTM00A51E47 (6).
The laboratory-scale cross-flow ultrafiltration SPIRALB system from TAMI
Industries (France) was used with ceramic membrane (an effective area of
0.006358 m2 and cut off 1 or 15 kDa). Volume of the feed solution was 0.3 L,
transmembrane pressure was 0.2 MPa. The experiments were performed with
retentate recycled into the feed vessel and permeate solution collected in the
permeate test-tube.
The aqueous solutions were analyzed for nickel(II) concentration by AAS using
a Polarized Zeeman Atomic Absorption Spectrophotometer Z-8200, HITACHI in
the air-acetylene flame.
Results and Discussion
In Fig. 2 are illustrated the surface tension isotherms for Cocamidopropyl
Betaine. The critical micelle concentration (CMC) is equal to 0.02 g/L. So low
value of CMC is favorable because of the amount of surfactants which should
be added in the micellar enhanced ultrafiltration. For comparison - CMC of
sodium dodecyl sulfate (SDS) is equal to 2.26 g/L (7), which is over a hundred
times more.
Foaming ability is a typical property of surfactant solutions. The ability to
produce foam is of a great importance in cosmetics and household products,
but is undesirable in micellar enhanced ultrafiltration. Liquids that create foam
58
introduce air into the pump and pump cavitation due to air aspiration is
observed. This phenomena is often a problem in MEUF. The main factor
determining the stability of the foam is the liquid drainage rate.
Fig. 2. Surface tension isotherm of Cocamidopropyl Betaine, c in g/L
CANCELLED
The volume of foam aqueous solutions of Cocamidopropyl Betaine is presented
in Fig. 3. The ability of the foaming of surfactant solution decreases with
addition of electrolyte (sodium chloride). The graph also shows that height of
foam column is much lower for salt solutions then for aqueous solutions
regardless of the time of measurement.
Fig. 3. Volume of foam for Cocamidopropyl Betaine solutions, square - water, circle 0.01 M NaCl, triangle - 0.05 M NaCl, diamond - 0.2 M NaCl, star - 2 M NaCl
The retention (R) of nickel(II) ions in the ultrafiltration process depends on the
type of membrane and surfactants used in experiments. The results are
presented in Fig. 4. The pore size of membrane has got high impact on the
value of R: smaller cut off of membrane - higher retention of metal ions.
Moreover, the type of surfactant used is very important. The highest retention
factors were obtained for SDS or its mixture with the Cocamidopropyl Betaine. It
should be emphasized that an important advantage of using the binary system
was almost twice lower concentration of surfactants used in the mixture.
59
100.00
90.00
80.00
70.00
R [%]
60.00
50.00
40.00
30.00
20.00
10.00
0.00
1
2
3
4
5
CANCELLED
Fig. 4. Retention of Ni(II) ions, black bar – membrane 5 kDa, grey bar – membrane 15
kDa, composition of the aqueous phase: 1 – 0.05 g/L Ni(II), 2 - 0.05 g/L Ni(II) + 1 CMC
Cocamidopropyl Betaine, 3 - 0.05 g/L Ni(II) + 5 CMC Cocamidopropyl Betaine, 4 - 0.05
g/L Ni(II) + 5 CMC SDS, 5 - 3 - 0.05 g/L Ni(II) + 2.5 CMC Cocamidopropyl Betaine +
2.5 CMC SDS
Conclusion
The micellar enhanced ultrafiltration was perceived as a successful technique
for the removal of nickel(II) ions. The used mixed surfactant systems showed
better results for the removal of metal and also have economical advantage
over the single surfactant used. Studies indicate that Cocamidopropyl Betaine
may be used in ultrafiltration. Its application indicates its high retention
efficiency of metal ions, low CMC and its mild impact on the environment.
Acknowledgements: This research was supported with 03/32/DS-PB/0501.
References
1. F. Fu et al., J. Environ. Manage., 92 (2011) 407-411.
2. S. De, S. Mondal, in “Micellar Enhanced Ultrafiltration: Fundamentals & Applications”, CRC
Press, Boca Raton, USA 2012.
3. S. Herrwerth et al., Tenside Surfactants Deterg., 45 (2008) 304-8.
4. Human and Environmental Risk Assessment on ingredients of household cleaning products.
Cocamidopropyl betaine (CAPB), 2005.
5. Cosmetic intermediates mazidla.com: http://mazidla.com/index.php?page=shop.product
_details&flypage=flypage.tpl&product_id=91&category_id=2&vmcchk=1&option=com_virtue
mart&Itemid=100140.
6. M.J. Rosen et al., J. Am. Oil Chem. Soc., 46 (1969) 399-402.
7. K. Staszak et al., Sep. Sci. Technol., 47 (2012) 802-810.
60
FLOTATION, HYDROPHOBICITY AND BUBBLE ATTACHMENT
TO THE QUARTZ SURFACE IN THE PRESENCE OF
HEXYLAMINE
Przemyslaw B. Kowalczuk1, Jan Zawala2, Anna Niecikowska2, Kazimierz
Malysa2
1
Wrocław University of Technology, Division of Mineral Processing, Wybrzeże
Wyspiańskiego 27, 50-370 Wrocław, Poland,
2
Jerzy Haber Institute of Catalysis and Surface Chemistry Polish Academy
of Sciences, Niezapominajek 8, 30-239 Cracow, Poland
e-mail: przemyslaw.kowalczuk@pwr.edu.pl
Quartz flotation and wettability in the presence of amines have been
continuously investigated by many authors. Most attention has been paid to
show a role of long chain alkyl amines (e.g. dodecylamine) and only a few
papers discuss the influence of short chain alkyl amines on the flotation
performance and hydrophobicity of quartz (1-6). In this paper, the influence of
hexylamine (C6H15N, HexNH2), as an example of a short chain alkyl amine, on
the flotation behaviour and interfacial properties of quartz was investigated.
It was shown that quartz was slightly naturally hydrophobic mineral with contact
angle greater than zero, and did not float in distilled water (Fig. 1a). Quartz
started to float in the presence of HexNH2. Higher concentration of amine
enhanced the maximum recovery of quartz. It was also shown that flotation of
quartz was strongly affected by pH of aqueous solution of hexylamine (Fig. 1b).
The maximum recovery of quartz in the presence of amine was observed at pH
11. At lower and higher pHs the flotation performance decreased.
100
100
maximum recovery of quartz, %
maximum recovery of quartz, %
Hallimond tube 100-200 μm
80
60
40
20
Hallimond tube 100-200 μm
pH 10-11
0
0.0
water
HexNH2 1·10-3 mol/dm3
80
60
40
20
0
0.2
0.4
0.6
HexNH2 concentration,
(a)
0.8
1.0
0
2
4
6
8
10
12
14
pH
mmol/dm3
(b)
Fig. 1. Influence of concentration (a) and pH of aqueous solution of hexylamine (b) on
the maximum recovery of quartz
A lack of quartz flotation in distilled water can be explained by presence of the
stable liquid film between the bubble and quartz surfaces, due to the repulsive
61
electrostatic interactions between negatively charged quartz and air bubble
surfaces. This hypothesis was confirmed in series of experiments on kinetics of
the three-phase contact (TPC) formation by the bubbles colliding with quartz
surface.
It was shown that in distilled water the three-phase contact (TPC) was not
formed. The TPC was formed in the presence of hexylamine and time of the
TPC formation (tTPC) at the quartz surface by the colliding bubble was affected
by the HexNH2 concentration and pH of solution. At pH lower than 4 and higher
than 12 the TPC formation was not observed. The TPC of the quartz/air
bubble/hexylamine was formed at pH 4-12 and the tTPC decreased with
increasing pH (Fig. 2). Rupture of the liquid film formed between the bubble and
quartz in the HexNH2 aqueous solutions of pH 4-12 was most probably not
caused by the solid surface hydrophobization but rather by adsorption of
hexylamine (non-dissociated RNH2 and dissociated RNH3+ forms) on the bubble
surface. The contact angle measurements showed that variations of both pH
and hexylamine concentration did not cause any significant variations of the
natural hydrophobicity of quartz. A correlation between efficiency of flotation
and the tTPC values was observed. The tTPC values were the shortest within
similar pH region where the quartz recovery was the highest (Figs. 1b and 2).
However, the mechanism of hexylamine action in TPC formation and quartz
flotation is still unclear and needs to be investigated.
no TPC
no TPC
2e-4 M
1400
time of TPC formation, ms
1200
1000
800
600
400
200
0
0
2
4
6
8
10
12
14
pH
Fig. 2. Influence of pH of aqueous solution of hexylamine on time of three-phase
contact (TPC) the quartz/air bubble/hexylamine formation
This work was partially financed by the National Science Centre Research Grant
(2012/07/D/ST8/02622). Financial support by the fellowship financed by the Foundation for
Polish Science (FNP) is also greatly acknowledged.
References
1. J. Laskowski, J.A. Kitchener, J. Colloid Interface Sci., 29 (1969) 670-679.
2. O. Sahbaz, A. Ucar, B. Oteyaka, Miner. Eng., 41 (2013) 79-85.
3. D.W. Fuerstenau et al., Trans. AIME, 229 (1964) 321-323.
4. G. Ghigi, Trans. IMM, 78 (1968) C212-C219.
5. S. Takeda, I. Matsuoka, Colloids Surf., 47 (1990) 105-115.
6. P.B. Kowalczuk, Int. J. Miner. Process., 140 (2015) 66-71.
62
NEW, POLAR POLYMERIC ADSORBENTS FOR THE
IMPROVEMENT OF PHENOLS SORPTION
Andrzej W. Trochimczuk, Anna Jakubiak-Marcinkowska, Sylwia Ronka
Faculty of Chemistry, Wrocław University of Technology, Wybrzeże
Wyspiańskiego 42, 50-370 Wrocław, Poland
e-mail: andrzej.trochimczuk@pwr.edu.pl
Adsorption on polymeric materials, called also solid-phase extraction, is
considered to be the most useful technique for removal of organics from liquid
samples. This is mainly due to the simplicity of operation, easy scaling-up and
also due to the availability of different sorbents. However, useful as they are the
sorbents suffer from the lack of high capacity and selectivity. For example –
adsorbents based on molecular imprinting possess extremely high selectivity
but very low capacity, whereas adsorbents obtained from styrenedivinylbenzene copolymers can have high capacity but low selectivity. Another
problem is the sorption of polar, hydrophilic adsorbates from aqueous solutions.
In such case the sorption on traditional adsorbents is low and in order to
improve capacity it was necessary to synthesize adsorbents with strongly polar
groups, such as nitrile, ester etc. The nitrogen or oxygen atoms with their
electron pairs can be involved in the formation of hydrogen bonds, dipole-dipole
interaction and thus increase the sorption capacity of phenol and its derivatives,
alcohols, acids etc. In such adsorbents the increased content of polar mers was
always at the expense of crosslinker (such as divinylbenzene) and thus
polymers rich in polar groups had lower specific surface area.
In this work we present preparation and properties of crosslinked polymers
obtained in suspension polymerization of allyl methacrylate and divinylbenzene
in the presence of inert solvents. These polymers display relatively high specific
surface area regardless of the crosslinker level. Thus, specific surface area is
477, 445, 409 and 421 m2/g for polymers with the nominal crosslinking degree
50, 40, 30, 20 wt.%, respectively. Sorption of o-, m-, p-nitrophenol, o-, m-, pchlorophenol, hydroquinone, catechol, resorcine and pyrogallol will be
presented and compared within the series of adsorbents.
Acknowledgements: project supported by the statutory grant from Faculty of Chemistry,
Wrocław University of Technology.
63
64
III. POSTERS
COMPARISION OF TRANSPORT OF ZINC AND IRON IONS
THROUGH POLYMER INCLUSION MEMBRANES (PIM) IN
SANDWICH TYPE MODULE AND GLASS PERMEATION CELL
Monika Baczyńska1, Marta Kołodziejska2, Magdalena Regel-Rosocka1,
Cezary Kozłowski2, Maciej Wiśniewski1
1 Poznań
University of Technology, Institute of Chemical Technology and
Engineering, Berdychowo St.4 , 60-965 Poznań, Poland,
2 Jan Długosz University in Częstochowa, Faculty of Mathematics and Natural
Sciences, Armii Krajowej Av. 13/15, 42-218 Częstochowa, Poland
e-mail: monika.z.baczynska@doctorate.put.poznan.pl
Polymer inclusion membranes (PIMs) represent an alternative to liquid-liquid
extraction (SX) for the removal of metal ions from aqueous solutions. These
membranes are formed by casting solution containing a polymer matrix, a
plasticizer and a carrier (1). Recently, phosphonium ionic liquids are frequently
used for separation of metal ions both in extraction and adsorption systems.
Many workers proposed application of these compounds as carriers of Zn(II)
and iron ions through PIMs (2,3).
This work aims at comparison of transport of zinc and iron ions through PIMs in
sandwich type module and glass permeation cell. As the metal ion carriers were
used three phosphonium ionic liquids, i.e. trihexyltetradecylphosphonium
chloride (Cyphos IL 101), trihexyltetradecylphosphonium bis(2,4,4trimethylpentyl)phosphinate (Cyphos IL 104), tributyl(tetradecyl)phosphonium
chloride (Cyphos IL 167). The obtained results showed that better results of
initial flux and permeability coefficient were noted in sandwich type module than
a glass permeation cell. In the case of the transport of Zn(II) and Fe(III) in
sandwich type module after 72 h over 90% of initial amount of zinc and iron(III)
were extracted to the membrane. It is noteworthy that the transport of Fe(II) was
ineffective in both types of modules (recovery factor not exceed 10%). The
reason for an advantage of transport in the sandwich type module over glass
permeation cell lies in obtained better results of transport parameters.
Acknowledgements: Monika Baczynska was financially supported within the project “Engineer
of the Future. Improving the didactic potential of the Poznan University of Technology”POKL.04.03.00-00-259/12, implemented within the Human Capital Operational Program, cofinanced by the European Union within the European Social Fund.
This work was supported by the 03/32/DS-PB/0501 grant.
References
1. M. Inĕs et al., J. Membr. Sci., 415-416 (2012) 9-23.
2. D. Kogelnig et al., Monatsch. Chem., 142 (2011) 769-772.
3. M. Baczynska et al., Przem. Chem., 92/9 (2013) 1574-1576.
67
SORPTION OF HEAVY METAL IONS BY FLY ASH:
EXPERIMENTAL AND MODELING STUDIES
Justyna Ulatowska, Izabela Polowczyk, Anna Bastrzyk, Tomasz Koźlecki,
Joanna Franczak and Zygmunt Sadowski
Wrocław University of Technology, Faculty of Chemistry, Department of
Chemical Engineering, Wyb. Wyspiańskiego 27, 50-370 Wrocław, Poland
e-mail: anna.bastrzyk@pwr.edu.pl
The presence of heavy metals in natural water and subsurface aquifers
represents a serious threat for human health. Therefore, many efforts have
been made to remove heavy metal ions from water and wastewater using
various methods. The major methods involve adsorption, ion exchange,
nanofiltration, reverse osmosis, electrodialysis, precipitation–coagulation,
oxidation–precipitation, and biological treatment (1). Among them, adsorption
using a variety of low cost materials has been proven to be economical,
effective and easy for operation (2).
Fly ash is a powdery material generated from the combustion of coal and
biomass in power plants and has a pozzolanic property. Therefore it is a
valuable and desirable material. This product can be used as sorbent of heavy
metal ions from water and wastewater (3-5).
The aim of this study was to investigate the possibility of the utilization of fly ash
for the removal of Cr(VI), Cu(II) and Ni(II) ions from aqueous solutions. The
effect of metal concentration, pH, contact time and sorbent dosage was
investigated. Measurements were carried out using powder material from the
Zgierz power plant (Poland). Adsorption experiments were done in the pH range
4-12 at 25°C for 24 hours. The heavy metal ions and fly ash concentrations
were 10-1000 mg/L and 1-200 g/L, respectively. The experimental data fitted
the pseudo-second order kinetic model well. Moreover, it was suggested that
the Langmuir isotherm is more adequate than the Freundlich isotherm in
simulating the adsorption isotherms of Cr(VI), Cu(II) and Ni(II). The maximum
adsorption capacity was achieved for 10 g/L adsorbent-to-chromium ratio, being
16.7 mg/g; 10 g/L adsorbent-to-copper ratio, being 30.3 mg/g and 5 g/L
adsorbent-to-nickel ratio, being 74.0 mg/g.
The test results indicated that fly ash could be used as a cheap adsorbent for
the removal of heavy metal ions in aqueous solutions.
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. Y. Li et al., Sci. Total Environ., 407 (2009) 5780-5786.
2. I. Polowczyk et al., Environ. Geochem. Health, 32 (2010) 361-366.
3. H. Cho et al., J. Hazard Mater. B, 127 (2005) 187-195.
4. J. Aguilar-Carrillo et al., Chemosphere, 65 (2006) 2377-2387.
5. A. Papandreou et al., J. Hazard Mater., 148 (2007) 538-547.
68
ADSORPTION OF Cu(II) AND Ni(II) IONS ONTO GREEN TEA
LEAVES
Anna Bastrzyk, Izabela Polowczyk, Aleksandra Molenda, Tomasz Koźlecki,
Justyna Ulatowska and Zygmunt Sadowski
Chemical Engineering, Wyb. Wyspiańskiego 27, 50-370 Wrocław, Poland
e-mail: anna.bastrzyk@pwr.edu.pl
Over the past several decades, the exponential population and social civilization
expansion, sharp modernization and metropolitan growth, and continuing
progress of the industrial and technologies has largely contributed to the
contamination of groundwater and other water resources by toxic heavy metals
such as Cu2+, Pb2+, Cd2+, Zn2+, Ni2+ etc. (1-3). These heavy metals become very
toxic at high concentration and lead to several diseases (3). Therefore, removal
of heavy metals from effluents is essential not only to protect the water sources
but also for the protection of human health. Various technologies have been
proposed for removal of these compounds from wastewater, including
precipitation, ion exchange, evaporation, oxidation, electroplating and
membrane filtration (4). During over recent years adsorption with the use of a
number of inexpensive biosorbents has been widely studied as an alternative
and effective technology of heavy metals removal (5).
Tea is an aromatic beverage consumed by the largest number of people in the
world. In 2007 the global production was 3.6 million tones. From the coffee shop
or tea–processing factory large quantities of tea wastes are usually discarded
into the environment without any treatment causing environmental problems (6).
These waste have found application as low-cost sorbents for removal of heavy
metals because of containing some functional groups in their structure
responsible for metal binding (7).
In this work, spent green tea leaves were used as a low cost sorbent for
removal of Cu(II) and Ni(II) from aqueous solution. The sorbent was
characterized by scanning electron microscope image, FTIR analysis and zeta
potential measurements. The effect of pH, initial metal concentration, adsorbent
dosage and contact time for removal of Cu and Ni ions were studied. The
kinetic of removal of metals ions was described using a pseudo-second order
model, The biosorption followed the Langmuir adsorption isotherm.
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. K.Y. Foo, B.H. Hameed, Adv. Colloid Interface Sci., 159 (2010) 130-143.
2. A. Ghosh et al., Appl. Water Sci., 5 (2015) 191-199.
3. Y.H. Huang et al., J. Hazard Mater., 144 (2007) 406-411.
4. J. Sanchez et al., Polymer Bulletin, 70 (2013) 2633-2644.
5. F. Xiao et al., J. Environ. Manage., 90 (2009) 3105-3109.
6. M. Nandal et al., Int. J. Curr. Eng. Tech., 4 (2014) 243-247.
7. P.E Aikpkopodion et al., AEJTS, 2 (2010) 72-82.
69
FACILITATED TRANSPORT OF METAL IONS THROUGH
POLYMER INCLUSION MEMBRANES CONTAINING 1-ALKYL1,2,4-TRIAZOLES AS A CARRIERS
Bernadeta Gajda1, Radosław Plackowski2, Mariusz B. Bogacki2
1
Częstochowa Uniwersity of Technology, Częstochowa, Poland,
University of Technology, ul. Berdychowo 4, 60-965 Poznań
e-mail: Mariusz.bogacki@put.poznan.pl
2 Poznań
Polymer inclusion membranes are composed of three main ingredients: polymer
matrix, plasticizer and carrier. In PIM preparation, as a polymer matrix, cellulose
triacetate (CTA) and poly(vinyl chloride) (PVC) are the most commonly used. As
carriers, compounds able to create complexes with transported metal ions,
widely applied in extraction processes are used.
Carriers used in membrane processes have to be characterized by ability to
create complexes with transported metal ions. One of the carriers groups are
acidic extractants which create chelating complexes. However, the formed
complexes are relatively stable and therefore it is necessary to apply
concentrated acids as a receiving phase. Another possibility is application of
Lewis bases which create complexes with metal ions in a form of solvates. In
this case, carriers have to be characterized by the presence of atoms which
have a free pair of electrons. Most often they are nitric, sulfur or oxygen atoms.
One of such groups of compounds that potentially could be effective carriers are
azoles. In our previous papers(1), application of alkyl derivatives of imidazoles
as carriers of heavy metal ions was shown. The obtained results suggest that
other compounds from a group of azoles, for example alkyl derivatives of
triazoles, could be applied as selective carriers of heavy metal ions.
The aim of the work was investigation of 1-alkyl-1,2,4-triazoles as a carriers of
Ni(II), Co(II), Cu(II) and Zn(II) ions in transport through the polymer inclusion
membranes. Membranes composed of polymer matrix - CTA and plasticizer ONPOE. As a carrier, derivatives of 1,2,4-triazoles with alkyl chain of n=8, 9, 10
carbon atoms were used. As a feeding phase, water solutions containing
mixture of 4, 3, 2 of metal ions were used. Concentrations of individual metal
ions were equal 0.1 mol/dm3 and total concentration of chloride anions were
equal 2 mol/dm3. As receiving phase demineralized water was used.
Obtained results have shown that with increasing of alkyl chain length in alkyl
substituent, transport rate of ions through PIM decrease. Also selectivity of that
process is changing. It allows for selective separation of copper(II) and zinc(II)
ions from solution containing nickel(II) and cobalt(II) ions.
Acknowledgements: This work was carried out within the framework of NCN grant No.
7441/B/T02/2011/40
References
1. B. Gajda, A. Skrzypczak, M.B. Bogacki, Physicochem. Probl. Miner. Process., 46 (2011)
289-294.
70
THEORETICAL STUDIES ON TRI-OCTYLOAMINE (TOA), TRI-nBUTYL PHOSPHATE (TBP) AND 1-DECYL-IMIDAZOLE (IMID10)
USING MOLECULAR DYNAMICS SIMULATIONS
Mariusz B. Bogacki, Piotr Kujawski
Institute of Chemical Technology and Engineering, Poznań University of
Technology, ul. Berdychowo 4, 60-965 Poznań, Poland
e-mail: mariusz.bogacki@put.poznan.pl
Extraction solvents such as TOA, TBP and IMID10 belong to the significant
group of chemical compounds, which are used in many technological processes
for selective separation (1). Molecular modeling simulations combined with
quantum mechanics are commonly used to research behavior of extraction
solvents and to calculate interaction between extractant and solvent molecules
(2-4). Results of MD simulations are useful from the extraction point of view.
Before studying of extraction process of organic or cation complexes, it is of
primary interest to understand the behavior of extractants, and get an insight
into their structure, preferential conformations and associations, in relation with
possible solvation effects. Recently researcher’s attention is mostly paid on
description of the effects at the interface: water phase/organic phase (5,6).
Molecular dynamics studies on following extractants: TBP, TOA and IMID10 are
presented. First, the conformation of extractants was analyzed as a function of
their environment (in pure water or pure chloroform phase). Then the behavior
of extractants is analyzed at the chloroform/water interface and in the mixture
system of these two solutes. These simulations demonstrate strong adsorption
and orientational preference at the water/organic interface, related to their
amphiphilic nature. Polar parts of molecules are pointed towards the aqueous
phase and alkyl chains are pointed to the organic one. Some of extractants
molecules are present in the organic phase what is related to their solubility.
Presented results are in good agreement with empirical studies and show that
molecular dynamics may be a useful tool in describing interfacial behavior.
03/32/DSPB/0509 conduced at the Poznan University of Technology. Calculations were carried
out in Wroclaw Centre of Networking and Supercomputing (http://www.wcss.wroc.pl), grant No.
227.
References
1. R.K. Mishra et al., Hydrometallurgy, 104 (2010) 298-303.
2. M. Bühl et al., J. Phys. Chem. B., 109 (2005) 18591-18599.
3. G. Chevrot et al, Phys. Chem. Chem. Phys., 8 (2006) 4166-4174.
4. S.M. Ali, et al., Desalination, 232 (2008) 181-190.
5. P. Kujawski, M.B. Bogacki, Sep. Sci. Technol., 47 (2012) 1285-1295.
6. H. Zheng et al., Comput. Theor. Chem., 970 (2011) 66-72.
71
IONIC LIQUID-ASSISTED EXTRACTION AS A SAMPLE
PREPARATION TECHNIQUE FOR HPLC
DETERMINATION OF BIOLOGICALLY ACTIVE
ALKALOID GALANTAMINE IN LEUCOJUM AESTIVUM
L. (SUMMER SNOWFLAKE)
Rozalina Keremedchieva, Ivan Svinyarov, Milen G. Bogdanov
Faculty of Chemistry and Pharmacy, University of Sofia St. Kl. Ohridski,
1, James Bourchier Blvd., 1164 Sofia, Bulgaria
e-mail: mbogdanov@chem.uni-sofia.bg
Galantamine (Nivalin, Razadyne, Reminyl or Lycoremine) is a biologically active
alkaloid used for the treatment of mild to moderate Alzheimer's disease and
various other memory impairments, in particular those of vascular origin.
Leucojum aestivum L., commonly named as Summer snowflake, is a plant
which is widely cultivated as an ornamental species, but it is also the main
source for the industrial production of galantamine. Therefore an appropriate
method for determination of this alkaloid in the plant material is desired. The
current protocol consists of sequential extractions with acidic (H2SO4) aqueous
solution and its implementation takes more than 15 h.
In order to improve the extraction step we studied a series of hydrophilic 1-alkyl3-methylimidazolium-based ionic liquids (ILs) as additives instead of H2SO4 in
the extraction of galantamine from plant material of L. aestivum. The extractions
were carried out both under ultrasonic and conventional heating conditions and
the extraction efficiency was monitored by HPLC analysis. The influence of the
anion, alkyl chain length in the imidazolium ion, IL concentration, extraction
time, particle size and solid-liquid ratio on the extraction efficiency was
comprehensively investigated. As a result, optimal conditions for quantitative
extraction of galantamine with 5% aqueous solution of 1-butyl-3methylimidazolium chloride {[C4C1im]Cl} were found. The system under study
was shown to provide the same extraction efficiency in comparison with the
conventional method, but with significant reduction in extraction time (from 15 h
to 1 h). The data obtained resulted in the development of an analytical
procedure for determination of galantamine in plant material of L. aestivum. This
could be of a great importance from an industrial standpoint due to the faster
and safer nature of the proposed method.
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.
72
CAPACITIVE DEIONIZATION METHOD FOR EXTRACTION OF
LITHIUM
Marek Bryjak, Anna Siekierka, Jan Kujawski
Wrocław University of Technology, Faculty of Chemistry, 50-370 Wrocław, Wyb.
Wyspiańskiego 27, Poland
e-mail: marek.bryjak@pwr.edu.pl
Capacitive Deionization (CDI) is an alternative method for water desalination.
The features of the method, mentioned in almost each paper, are its
robustness, energy efficiency and operation easiness. However, the gross of
the attempts were focused on water demineralization. The extraction of valuable
ions from diluted solutions was of lower interest. Lately, few papers dealing with
recovery of lithium from aqueous solutions have been published.
Here we present our studies on harvesting of lithium from brackish water by
means of two systems: CDI with lithium selective electrode and CDI equipped
with Li-selective membrane covering the electrodes. The first system consisted
of hybrid electrodes with λ-MnO2 blended with activated carbon. It was noted
that lithium chloride capacity passed the maximum value for electrodes with
20% of manganese oxide. For larger amounts, the electrodes adsorbed lithium
salt less efficiently and worked instable. Additionally, some brownish spots were
determined on the electrode surfaces. They resulted from action of chlorine
oxides that were formed during the process and oxidized the electrode
components. The second investigated system consisted of neat carbon
electrodes sandwiched with ion-exchange membranes. The lithium selective
membrane was synthesized by means of plasma induced interpolymerization of
(meth)acrylic monomers into pores of supporting Celgard 2400 membrane. Two
functional polymers were selected to participate in transport of lithium ions.
They were poly(di(ethylene glycol)methyl ether methacrylate) and poly(glycidyl
methacrylate) modified with hydroxymethyl-12-crown-4. It was found that the
sorption of lithium chloride took the largest value for membrane with copolymers
of acrylic acid and glycidyl methacrylate modified with crown ether, and that
membrane was better than membranes containing sole poly(acrylic acid) or
poly(glycidyl methacrylate derivative).
73
PAPRIKA WASTE AS A BIOSORBENT FOR REMOVING HEAVY
METALS FROM AQUEOUS SOLUTIONS
Ryszard Cierpiszewski1, Joanna Dudczak1, Tomasz Kalak1, Keisuke Ohto2
1 Poznań
University of Economics, Faculty of Commodity Science,
al. Niepodległości 10, 60-967 Poznań, Poland,
2 Saga University, 1-Honjo, Saga 840-8502, Japan
e-mail: r.cierpiszewski@ue.poznan.pl
The contamination of heavy metal ions in wastewater is a growing
environmental concern as it is associated with the health risks to human lives.
There are several methods to remove the toxic metals from wastewater e.g.
chemical precipitation, coagulation, membrane separation, ion-exchange, and
adsorption. Biosorption seems to be a new and suitable wastewater technology
to remove heavy metals because it uses cheap and environmentally-friendly
biomaterials as agricultural by-products (1).
Paprika is a source of biologically active compounds and it contains resins,
pentosans, cellulose, protein, pungent principles, colouring pigments, mineral
elements and small amounts of volatile oil. All the ingredients exhibit various
benefits in relation to human health but also to sorption properties of heavy
metal ions (2). Paprika waste is generated in food industry and is used as
biomaterials for metal removal. The aim of our research is to investigate the
adsorption conditions of Cu(II) and Cd(II) metal ions onto dried paprika
residues.
Paprika waste was obtained from agriculture industry. The crude material was
ground, dried in 60°C, and stored in a desiccator. The adsorption experiments
were carried out in batch conditions at room temperature. Copper(II) and
cadmium(II) concentrations in the aqueous phase were measured by atomic
absorption spectroscopy. The experiments were carried out at pH 2 - 5.
The obtained results show that the adsorption of both ions increases with
increasing metal concentration in aqueous solutions. Both ions were
significantly bound to paprika waste, which was also confirmed by FT-IR
measurements. The effect of contact time on the metal ions was studied at pH
4. The rate of both metal ions removal became almost insignificant after 30 min.
The influence of pH on the adsorption of the studied metals ions on paprika
shows that the adsorption ability depends strongly upon the pH of the aqueous
solution. The removal of both ions increased with increasing pH. The effect of
particle size on the adsorption was also studied. The finest fraction achieved the
highest adsorption in comparison with other larger particles, which was also
confirmed in literature.
The obtained results suggest that paprika waste has possibility to be used as
effective adsorbent for copper and cadmium ions removal.
References
1. M.A. Hubbe et al., Bioresorces, 6(2) (2011) 2161-2287.
2. A.N. Tepić et al., APTEFF, 39 (2008) 77-83.
74
ADSORPTION OF Cu(II) FROM AQUEOUS SOLUTIONS ON
GELATIN-SILOXANE HYBRID MATERIALS
Ryszard Cierpiszewski1, Patrycja Wojciechowska1, Hieronim
Maciejewski2,3
1 Poznań
University of Economics, Faculty of Commodity Science,
al. Niepodległości 10, 60-967 Poznań, Poland,
2 Adam Mickiewicz University, ul. Umultowska 89b, 61-614 Poznań, Poland,
3 Poznań Science and Technology Park, Adam Mickiewicz University
Foundation, ul. Rubież 46, 61-612 Poznań, Poland
e-mail: r.cierpiszewski@ue.poznan.pl
Synthesis of organic-inorganic hybrids offers the possibility of combining the
advantages of organic polymer (elasticity, formability) and inorganic material
(hardness, strength, high chemical resistance and thermal stability). This
approach makes hybrid materials suitable for several applications: in textile,
packaging, construction, automobile industries, as well as in micro-optics,
microelectronics, synthesis of functional coatings, and as biosensors,
biocatalysts or novel materials for cosmetics or biomedical purposes (1,2).
We developed porous hybrid materials based on gelatin and organomodified
silicones containing epoxy- and both, epoxy-, as well as, fluoroalkyl-groups and
applied them for adsorption of Cu(II) from aqueous solution. Gelatin was
chemically modified in the reaction of its functional groups with oxirane ring of
chosen siloxane. Gelatin as an ionic hydrophilic linear polymer shows excellent
water solubility, non-toxicity and biodegradability, and has functional groups
(-NH2 and -COOH) capable of adsorbing metal ions. Unfortunately, gelatin
exhibits poor mechanical properties, which limit its application. Organomodified
silicones have been used to improve the mechanical strength of gelatin and its
functional properties. Obtained materials, due to their large specific surface
area, the presence of chemical groups having strong affinity to metal ions, and
appropriate mechanical strength, could be successfully applied to metal ions
adsorption.
Here we demonstrate how type and amount of the organomodified silicone used
for the modification of gelatin affected the adsorption properties of the hybrid.
The effect of pH of aqueous solutions and concentration of metal ions were also
studied. The removal of metal ions on the modified gelatin was carried out in
batch conditions at room temperature. Cu(II) concentration in the aqueous
phase was measured by atomic absorption spectroscopy.
References
1. G.L. Drisko, C. Sanchez, Europ. J. Inorg. Chem., 32 (2012) 5097-5105.
2. K. Tsuru, S. Hayakawa, A. Osaka, J. Sol-Gel Sci. Technol., 32 (2004) 201-204.
75
NEW CORE-SHELL TYPE POLYMERIC SUPPORTS BASED ON
THE AMBERLITE XAD-4 ADSORBENT
Piotr Cyganowski, Dorota Jermakowicz-Bartkowiak
Faculty of Chemistry, Division of Polymer and Carbonaceous Materials,
Wroclaw University of Technology, Wyb. Wyspianskiego 27, 50-370 Wroclaw
e-mail: piotr.cyganowski@pwr.edu.pl
The most popular supports for preparation of ion-exchange resins in form of
polymeric beads are various types of polystyrene (S) and divinylbenzene (DVB)
copolymers. A preparation of that type of materials requires in a first step,
copolymerization of styrene (S) and divinylbenzene (DVB) to form a crosslinked
suspension copolymer, S/DVB (1). Usually, the process is followed by
introduction of reactive sites (chloromethyl groups) into polymer structure using
bis-chloromethyl ether (BCME) as an alkylating agent. Due to the strongly
carcinogenic character of the BCME, the new core-shell type polymeric
supports with accessible chloromethyl groups were synthesized (2).
The new resins, coded as 1T, 1TD, 2T and 2TD were synthesized in course of
an impregnation of a commercial Amberlite XAD-4 adsorbent using different
mixtures of vinylbenzyl chloride and divinylbenzene. The monomers were
further polymerized within the structure of the polymer carrier creating
Interpenetrating Polymer Networks (IPN). The syntheses have been evaluated
by recording FT-IR spectra, as well as analyzing the sorption and desorption of
nitrogen at 77 K. Furthermore, captured SEM micrographs allowed to observe
significant changes in the initial XAD-4 matrix morphology.
XAD-4
2T
2TD
Fig. 1. Captured SEM micrographs of the Amberlite XAD-4 adsorbent, and the resins 2T, 2TD
Based on the obtained results, the reactive chloromethyl groups were
successfully introduced into XAD-4 structure. Captured SEM micrographs,
displayed in the Figure 1, revealed that VBC/DVB copolymer has covered initial
polymeric base allowing to determine techniques that lead to receive that effect.
Acknowledgements: This 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.
References
1. F. Helfferich, “Ion Exchange”, General Publishing Co., Toronto 1995.
2. M. Concha-Barrientos et al. in: “Comparative quantification of health risk”, Eds. M. Ezzati;
WHO, Geneva 2004.
76
ECOFRIENDLY LOW-COST NATURAL BIOSORBENTS
TOWARDS RECOVERY OF GOLD
Dorota Jermakowicz-Bartkowiak, Piotr Cyganowski
Faculty of Chemistry, Division of Polymer and Carbonaceous Materials,
Wroclaw University of Technology, Wyb. Wyspianskiego 27, 50-370 Wroclaw
e-mail: piotr.cyganowski@pwr.edu.pl
The development of new low cost and selective technologies for noble metals
recovery from industrial effluents is reasonable from an economic and
environmental points of view. Biosorption is currently considered as one of the
most promising technologies that can be used for the recovery of precious
metals as well as the removal of toxic or pollutant ones. The use of natural
biosorbents based on a type of waste-biomass or numerous plants, that are
available in a local environment, would be profitable in the recovery and
preconcentration of gold(III) ions from city, mine or electronic wastes. A
biosorption-based processes offer a number of advantages including low
operating costs, minimization of the volume of chemical sludge to be handled
and high efficiency in detoxification of effluents.
In the present studies, the Golden Delicious apples, as one of the most
commercially successful apples of all the time, the Prunus Domestica most
popular European plum, the blackcurrant (Ribes nigrum), black forest berries
(Caccinium Myritillus), tomatoes, carrots and potatoes were used. Fresh
samples of natural biosorbents were bought or collected in the regional market.
Pomaces of apples, blackcurrants, plums, tomatoes, carrots, potatoes and
bilberry were dried at 30°C. Next, they were grinded and the research materials
were sieved through a sieve of 20 mesh size in order to standardize their
dimensions. Sorption of gold tests were carried out using a batch procedure. An
accurate weight of 0,05 g of a dry solid was equilibrated with 20 ml of an
aqueous solution containing Au(III) ions (10 mg/dm3) in the presence of 0.1 M
HCl.
The best results of gold sorption (100%) from diluted solutions in 0.1 M HCl
revealed polish fruits from Lower Silesia district i.e. apples, plums, black
currants and bilberries. Biosorption of Au(III) onto apples was a rapid process
with more than 90% removal at the initial 15 min. Moreover it was observed that
the Au(III) ions, loaded on apples pomace could be converted into an elemental
gold which was confirmed by SEM/EDS analysis. The process of gold sorption
can be described as a reduction coupled loading. The mechanism may include
two steps, i.e. electrostatic interactions between AuCl4- complex and the
positively charged hydroxyl and phenyl-hydroxyl groups present in plants and
oxidation of these moieties to carbonyl groups, generating the elemental gold.
Acknowledgements: This work was financed by a statutory activity subsidy from the Polish
Technology.
77
CROSS-LINKED HORSERADISH PEROXIDASE BY MODIFIED
BIO-IMPRINTING PROCESS FOR IMMUNOASSAYS
Joanna Czulak1, Antonio Guerreiro2, Karima Metran2, Francesco
Canfarotta2, Andrzej Trochimczuk1, Sergey Piletsky2
of Chemistry, Wrocław University of Technology, Wybrzeże
Wyspiańskiego 42, 50-370 Wrocław, Poland,
2 Department of Chemistry, University of Leicester, University Road, Leicester,
LE1 7RH, UK
e-mail: joanna.czulak@pwr.edu.pl
1 Faculty
Diagnostic assays are some of the most important tools in healthcare,
influencing around 70% of all medical decisions (1). Developments
in diagnostics have the potential to improve the efficiency of early detection and
prevention of chronic and acute disorders (2). One of the largest contributors
to clinical diagnostics is immunochemical analysis, which represents 36% of the
global IVD market and is worth $15.8 bln (3). This is the reason why there
is a big demand for development of new diagnostic tools used
in immunoassays.
In this work we present preparation of cross-linked Horseradish Peroxidase
in the presence of immobilised template using a modified bio-imprinting
approach, in order to introduce specificity for model drug template (vancomycin)
(4). The proposed method would not require any derivatisation, precipitation,
lyophilisation and use of organic solvent. In our method the model enzyme
(HRP) was cross-linked using glutaraldehyde (GA) in the presence of glass
beads (solid phase) bearing immobilised template such as vancomycin or
ampicillin. The standard bio-imprinting processes produce temporary
recognition sites which are unstable and sensitive to moisture and changes in
pH and ionic strength (5,6). The modified cross-linking process improved the
stability by 6°C (comparing with the native enzyme) and creates permanent
specific recognition sites. The developed constructs are interesting objects for
immunoassays since they combine catalytic properties of enzymes and binding
properties of antibodies. To prove it, we demonstrated a novel form of ELISA
where HRP imprinted with vancomycin and ampicillin replaced traditional
enzyme-antibody conjugates for selective detection of the templates at
micromolar concentrations.
Acknowledgements: Project supported by Wroclaw Centre of Biotechnology, programme The
Leading National Research Centre (KNOW) for years 2014-2018.
References
1. P. Przywara, Economic Papers 417, European Commission, Directorate-General for
Economic and Financial Affairs, 2010.
2. In Vitro Diagnostic (IVD) Market, Technique & Applications – Forecast To 2017,
MarketsAndMarkets, 2015.
3. J. Witonsky, Genet. Eng. Biotechn. N., 32 (2012) 14.
4. A. Poma et al., Adv. Funct. Mater., 23 (2003) 2821-2827.
5. F. Peissker, et al., Bioorg. Med. Chem., 7 (1999) 2231-2237.
6. A. Copolongo, et al., J. Chem. Technol. Biotechnol., 78 (2002) 56-63.
78
A NEW POLYMERIC SORBENT FOR REMOVAL OF MERCURY
IONS FROM AQUEOUS SOLUTIONS
Erdem Yavuz, İrem Çokgez, B. Filiz Şenkal
Department of Chemistry, Istanbul Technical University, Turkey.
e-mail: yavuzerd@itu.edu.tr
Mercury is used in a wide variety of industries such as fungicides, electrical
paints, chlor-alkali, paper and pulp, pharmaceutical, etc. (1). All mercury
compounds show high toxicity so the extraction of mercuric ions from aqueous
wastes and drinking water are of special environmental importance. Polymers
carrying functional groups, especially metal chelating groups (so-called
polymeric sorbents) offer excellent metal-uptake abilities, and they have been
discussed in many articles and reviews (2,3).
A new polymeric resin with amide-sulfonamide functions has been prepared for
the extraction of mercuric ions. Crosslinked sulfonamide based resin was
prepared starting from reaction with chlorosulfonated polystyrene and excess of
tris(2-aminoethyl)-amine and then the resulting resin was reacted with excess
acetyl chloride to give an amide - sulfonamide resin (Scheme 1).
The amide containing polymeric sorbent was an efficient sorbent to remove
mercury. The mercury sorption capacity of the sorbent is around 1.90 mmol/g
under non-buffered conditions. Mercury adsorption experiments were also
carried out at various pH’s and according to the results obtained mercury
adsorption capacity of the resin increased with increasing pH.
-
NH2
O
P
O
N
S NH
+
NH2
CH3-C-Cl
O
Triethylamine
O
NH C
O
P
S NH
NH2
N
NH C
O
NH2
O
Scheme 1. Preparation of Sorbent
References
1. D. Mohan et al., Colloids Surf., A, 177 (2000) 169-181.
2. S.D. Sahni et al., Coord. Chem. Rev., 59 (1984) 1-139.
3. S. Dutta et al., J. Hazard. Mater., 172 (2009) 888-896.
79
POSSIBLE MECHANISMS OF THE WATER TREATMENT WITH
ALUMINO-SILICIC REAGENT
D. Y. Feklistov1, I. M. Kurchatov2, N. I. Laguntsov2
1
JSC Aquaservice, 115409 Kashirskoe sh. 31, Moscow, Russian Federation,
National Research Nuclear University MEPhI, 115409 Kashirskoe sh. 31,
Moscow, Russian Federation
e-mail: aquaserv@mail.ru
2
Various methods of water purification are used. The reagent treatment of water
is the most common and available, using coagulants and flocculants. Some
cleaning methods use nanomaterials, mesoporous materials that act as
reagents. The efficiency of water purification due to the intensification of colloid
- chemical processes in the liquid phase (formation of a new phase,
coagulation, flocculation, adsorption).
In this technology it is proposed to use as a reagent complex alumino-silicic
reagent, containing aluminum sulfate and active silicic acid. It is known, that the
effectiveness of aluminum sulfate as coagulant is limited by coagulating ability
of aluminum hydroxide. Flocculation effect of the active silicic acid is based on
mutual coagulation of oppositely charged particles, also molecules of active
silicic acid are condensation products centers of coagulant (1). The interactive
mechanism of alumino-silicic reagent components with impurities contaminated
water is based also on mutual coagulation and charged particles impact on the
primary flocs. Under certain conditions as a result of their further interaction,
flocculation is occurred (consolidation of destabilized particles, cross-bonding
between the particles) and the formation of alumino-silicic structures are
formed, with the capture of the pollutants.
High efficiency of the alumino-silicic reagent is conditioned, on the one hand, by
additive properties of components of the composite and on the other hand, by
forming mesoporous alumino-silicic structures, with hi-developed interfacial
surface and a high adsorption capacity (2).
Dynamics of synergetic effect in the alumino-silicic reagent is studied badly.
However, it is assumed that initially nanostructures are formed like the cell,
further structures become larger, as the result of process of self-organization,
more sophisticated spatial three-dimensional structure area is formed, with
higher flocculation ability. Thus, the urgent task is to explore the process of selforganization alumino-silicic structures and the nanoparticles ensembles
formation. The solution of these problems will allow determining the optimal
conditions for the organization of the water-treatment process.
Acknowledgements: The work was financially supported by the Ministry of education of Russian
Federation, agreement № 14.575.21.0086 dated 20 October 2014.
References
1. E.D. Babenkov, Water treatment coagulants. Nauka, Moscow, 1977.
2. N.I. Laguntsov, Y.P. Neschimenko, D.Y. Feklistov in «Rusnanotech 08», Moscow 2008, 609611.
80
INFLUENCE OF TEMPERATURE ON TRANSPORT OF Ni(II),
Co(II), Cd(II) AND Zn(II) THROUGH POLYMER INCLUSION
MEMBRANES
Bernadeta Gajda1, Mariusz B. Bogacki2
1
Częstochowa University of Technology, Częstochowa, Poland,
University of Technology, ul. Berdychowo 4, 60-965 Poznań, Poland
e-mail: gajda@wip.pcz.pl
2 Poznań
Recently, polymer inclusion membranes (PIM) are the objects of intensive
investigation in many research centers. This situation results from the possibility
of a broad choice of the membrane composition as well as their relatively good
stability.
In the preparation of PIM, cellulose triacetate (CTA) and poly(vinyl chloride)
(PVC) are the most commonly applied matrices. Besides these two basic
polymers other polymer matrices are used, for example: cellulose derivatives,
poly(vinyl fluoride) or poly(vinylidene fluoride). On the proper selection of
polymer influence his ability to dissolving in suitable solvent and compatibility
with other membrane components. Also, kind of applied matrix influences the
transport properties and mechanical stability of prepared membranes.
Important ingredients applied in membrane are ion-selective carriers. Their
proper choice determines the rate of process as well as the membrane ability to
selective separation of ions occurred in the processed solutions. As a carries,
the compounds able to complex formation with the metal ions are used. Most
often they are acidic extractant such as derivatives of phosphoric acid or
oximes. Also the Lewis bases could be applied. In that case the amines and
pyridine derivatives are the most often used. Other heterocyclic aromatic
compound contained nitrogen – azoles can be applied too.
The aim of this study was to investigate influence of temperature on Ni(II), Co(II)
and Zn(II) ions transport through the polymer inclusion membranes, from
chloride solutions containing totally 2 mol/dm 3 of chloride anions.
1-alkylimidazoles were used as a carrier of the metal ions. Concentration of
individual metal ions were equal: Co(II), Ni(II), Zn(II) – 0.01 mol/dm3 and Cd –
0.005 mol/dm3. As a feeding phase, solutions containing mixture of 4, 3 and 2
ions were applied. As a receiving phase, demineralized water was used.
In presented studies polymer inclusion membranes composed of CTA and 1alkylimidazoles with alkyl chain length equal n=8, 10 and 12 carbon atoms as a
carriers were applied. Research was carried out in the temperatures equal to:
25, 35 and 45°C. Obtained results allow to determine the influence of
temperature on transport selectivity of metal ions through the PIM.
Acknowledgements: This work was carried out within the framework of NCN grant No.
7441/B/T02/2011/40.
81
SEPARATION OF WATER/ALCOHOL MIXTURES WITH
CHITOSAN MEMBRANES
Magdalena Gierszewska, Jadwiga Ostrowska-Czubenko
Nicolaus Copernicus University in Toruń, Faculty of Chemistry, Gagarina St. 7,
87-100 Toruń, Poland
e-mail: mgd@chem.uni.torun.pl
Membrane technology, due to its economic efficiency, has been widely used in
different processes, for example for purification, concentration and separation.
For the dehydration of organic solvents by pervaporation an attention has been
focused on different highly hydrophilic polymers that possess functional groups
able to interact with water molecules. Among them chitosan (Ch), a linear
polysaccharide composed of β-(1-4)-2-acetamido-2-deoxy-β-D-glucopyranose
and β-(1-4)-2-deoxy-β-D-glucopyranose units, has attracted an significant
attention as membrane material. It is not only due to its hydrophilicity but also
due to its facile chemical and physical modification, film forming properties and
good chemical and thermal resistance.
Moreover, chemically and physically modified chitosan was earlier used for the
preparation of membranes for metal-ion separation, gas separation, reverse
osmosis, ultrafiltration, etc. In medicine, chitosan membranes were proposed to
be applied as artificial kidney membrane and in drug delivery systems.
In the present study both non-modified chitosan membranes as well as chitosan
membranes modified by chemical crosslinking with glutaraldehyde (GA) were
prepared. Formation of chemical crosslinks between amino groups of chitosan
and aldehyde groups of GA was confirmed with FTIR spectroscopy. Using
scanning electron microscopy it was found that prepared membranes were
dense and non-porous. Separation properties of membranes in pervaporational
dewatering of water/alcohol mixtures was examined and compared. Twocomponent water/ethanol and water/propanol solutions of different composition
were used. It was found that water preferentially permeates through modified as
well as unmodified chitosan membranes. It was also verified that chemical
crosslinking affects membranes separation properties.
82
TRANSPORT PROPERTIES OF CHITOSAN AND ALGINIC
MEMBRANES APPLIED FOR PERVAPORATIVE DEHYDRATION
OF ETHANOL
Małgorzata Gnus1, Gabriela Dudek1, Roman Turczyn1, Artur Tórz1,
Krystyna Konieczny2
1
Silesian University of Technology, Faculty of Chemistry, Dapartment of
Physical Chemistry and Technology of Polymers, Gliwice, Poland,
2 Silesian University of Technology, Faculty of Energy and Environmental
Engineering, Institute of Water and Wastewater Engineering, Gliwice, Poland
e-mail: Malgorzata.Gnus@polsl.pl
In recent times pervaporation was mainly used for the dehydration of organic
solvents, e.g. alcohols, especially ethanol. There are many studies concerning
the development of homogeneous or heterogeneous membranes with high
performance for dehydration purposes. As hydrophilic polymers, which may be
used for membrane preparation, are chitosan (1-3) and alginate (4-6).
Blending polymers, similarly to crosslinking process, is one of polymer matrix
modification method, which can improve the efficiency of membranes without
significant sacrificing membrane selectivity.
The aim of this work was the comparison of separation properties of
membranes based on different polymers in the pervaporative dehydration of
ethanol. For this purpose membranes based on chitosan and/or alginate and
crosslinked in the same manner were prepared. Pervaporation experiments
were caried out at room temperature and then based on the determined total
flux and GC estimated concentration
the transport characteristics of
investigated membranes was evaluated. Selected crosslinking agents were
differently affected dependent on the used polymer matrices. The influence of
crosslinking species on the separation properties, physicochemical properties
and dehydration process efficiency was discussed.
Acknowledgements: The autors would like to thank the Silesia University of Technology for
providing financial support under the project BKM-/RCH4/2015.
References
1. G. Dudek et al., Sep. Purif. Technol., 133 (2014) 8-15.
2. G. Dudek et al., Sep. Sci. Technol., 47 (2012) 1390-1394.
3. S. Sunitha et al., Carbohyd. Polym., 87 (2012) 1569-1574.
4. S. Kalyani et al., Desalination, 229 (2008) 68-81.
5. M. Sarawathi et al., Desalination, 269 (2011) 177-183.
6. S. Kalyani et al., Ind. Eng. Chem. Res., 45(26) (2006) 9088-9095.
83
PERMEATION OF ETHANOL AND WATER VAPOURS THROUGH
CHITOSAN MEMBRANES WITH FERROFERIC OXIDE
PARTICLES
Gabriela Dudek, Małgorzata Gnus, Anna Strzelewicz, Monika, Krasowska,
Roman Turczyn, Artur Tórz
Silesian University of Technology, Faculty of Chemistry, Dapartment of Physical
Chemistry and Technology of Polymers, Strzody 9, 44-100 Gliwice, Poland
e-mail: Malgorzata.Gnus@polsl.pl
Membrane technology is considered as energy-efficient process for recovering
organic solvents from their dilute solutions. For the dehydration of ethanol a
serious attention has been focused on highly hydrophilic polymers like PVA,
chitosan and alginate. Nowadays modification of well-known polymeric
materials gives a better chance to find materials of good mechanical strength
and chemical resistance, good stability, high permeability and selectivity.
Chitosan is regarded as the effective water permselective material since
chitosan membranes have high separation factors (1). Furthermore modified
chitosan membranes (with magnetic powder) were successfully used to
dehydration of ethanol in pervaporation process (2). The authors observed that
permeation of water after addition of iron oxide nanoparticles to the polymer
matrix gradually increased. Magnetic powder (Fe3O4 particles) exhibits
a superparamagnetic properties what allows to separate water and ethanol.
In this paper, we propose chitosan membranes filled with different amount of
ferro-ferric oxide and cross-linked by different agents. We extend the previous
research (3) about next crosslinking-agent i.e. glutaraldehyde. To estimate the
influence of added magnetic powder on the separation properties of prepared
membranes, the permeation fluxes were determined and compared with the
values of crosslinked chitosan membranes without magnetite. The permeation
fluxes, both for ethanol and water, were determined based on the weight loss
method of a measuring vessel. Mass transport coefficients (diffusion,
permeation and solubility coefficients) were evaluated and the influence of
magnetic powder and cross-linking agents on ethanol and water permeation
was discussed. Change in permeation of water and ethanol, for analysed crosslinked chitosan membranes, after addition of magnetite was observed.
Acknowledgements: The authors would like to thank the Silesian University of Technology for
providing financial support under the project BKM-507/RCH4/2015.
References
1. K. Zielińska et al., Sep. Purif. Technol., 83 (2011) 114-120
2. G. Dudek et.al., Sep. Purif. Technol., 133 (2014) 8-15
4. G. Dudek et al., Sep. Purif. Technol., 109 (2013) 55-63.
6. J. Ren et al., Sep. Sci. Technol., 33(4) (1998) 517.
7. X.P. Wang et al., J. Membr. Sci., 119 (1996) 191-198.
8. S.H. Tan et al. AJSTD, 19(2) (2002) 69-83.
84
AUTOMATED SYNTHESIS OF MOLECULARLY IMPRINTED
POLYMER NANOPARTICLES
Antonio Guerreiro and Sergey Piletsky
Chemistry Department, University of Leicester, University Road, Leicester, LE1
7RH, UK
e-mail: ag398@le.ac.uk
Over the last decades Molecularly Imprinted Polymers (MIPs) have become an
important research target as well as an instrument for solving industrial needs in
separation and sensing. The work, however, is hindered by the poor
processability of bulk MIPs which cannot be easily integrated with sensors and
assays and the polyclonal nature of the binding sites in materials synthesised
using traditional approaches. These problems can be solved by manufacturing
MIPs in nanoparticle format, and combining synthesis with an affinity purification
step; the product of this process is comparable to natural antibodies and can be
employed for the same technical uses. However, up to now, there was no
instrument on the market capable of manufacturing MIP nanoparticles with the
quality and quantities required for most practical applications.
Here we describe the first automated synthesiser for manufacture of MIP
nanoparticles. The mode of operation of the instrument is based on the concept
of solid-phase molecular imprinting. Unlike “traditional” molecular imprinting
approaches where the target molecule (template) is free in solution, solid-phase
imprinting relies on template immobilised at the surface of a solid support. This
support is placed into the reactor and brought into contact with monomer
mixture. The polymerisation is then initiated, leading to formation of polymer
nanoparticles around the immobilised template. Post-synthesis, the solid
support functions as an affinity matrix for separation of imprinted nanoparticles
from remaining monomers and low affinity polymer. This process (synthesis and
subsequent affinity purification) can easily be automated and performed in a
computer-controlled instrument. Imprinted nanoparticles can be produced in
less than 3 hours, with high affinity/specificity to their target and a
homogeneous distribution of binding site affinities. Importantly, we have also
demonstrated that these materials can be used as direct replacement of natural
antibodies in a variety of sensors/assays.
85
PMMA-BASED SORBENTS FOR ZINC REMOVAL
Dominik Zdybał, Andrzej K. Milewski, Agata Jakóbik-Kolon
Silesian University of Technology, Faculty of Chemistry,
B. Krzywoustego 6, 44 – 100 Gliwice, Poland
e-mail: agata.jakobik@polsl.pl
Sorbents based on cross-linked poly(acrylic acid) (PAA) and poly(methacrylic
acid) (PMAA) are commonly used for heavy metals removal and dyes
separation (1-3). Nevertheless, PMAA based exchange resins show poor
selectivity toward zinc ions (4).
The objective of this work was to obtain a PMMA-based sorbent for zinc
removal. Poly(methyl methacrylate) was chemically modified. As a starting
material, we have considered uncross-linked PMMA differing in molecular
weight and tacticity. In the first step, PMMA has been dissolved completely in
diglyme (10% solution) and a 2-(2-methoxyethoxy)ethanol with a solid
potassium hydroxide was added. Afterward, a mixture of ethylene glycol with
dimethyl sulfoxide was introduced. Poly(ethylene glycol) may be used instead of
ethylene glycol. The mixture was being agitated till rapid gelation that usually
occurred after 5-10 min. The reaction of hydrolysis was carried out
predominantly not longer than 30 min. The temperature was maintained below
130°C. Obtained gel materials were then purified, dried and pulverised.
Our studies reveal novel, fast and environmentally friendly modification method
of high molecular atactic PMMA (350 000 - 1 000 000 Da). Not only obtained
materials possessed high sorption capacity, but also became chemically crosslinked that is essential for good sorbents properties. Obtained copolymers of
cross-linked potassium poly(methacrylate) and methyl methacrylate were then
tested for zinc ions uptake under various conditions (pH, zinc concentration,
temperature). Highly hydrolysed PMMA has been a subject of a second
modification step, due to the selectivity toward zinc ions improvement.
Research results for both modification steps will be presented in our poster.
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. J. Park, H.A. Dam, D. Kim, Korean J. Chem. Eng., 32(5) (2015) 967-973.
2. G.S/ Azhgozhinova et al., J. Colloid Interface Sci., 278 (2004) 155-159.
3. Z. Chunjiao et al., J. Nanosci. Nanotechnol., 13 (2013) 4627-4633.
4. P. Riveros and E.W. Wong, Metals removal from acid drainage by ion exchange, The Mine
Environment Neutral Drainage (MEND) Report 3.21.1(b), April 1995.
86
NEW, HYBRID PECTIN-BASED BIOSORBENTS
A. Jakóbik-Kolon, A. K. Milewski, K. Karoń, J. Bok-Badura
Silesian University of Technology, Faculty of Chemistry, Department of
Chemistry, Inorganic Technology and Fuels, ul. B. Krzywoustego 6,
44 -100 Gliwice, Poland
e-mail: agata.jakobik@polsl.pl
Wastewater containing heavy metal ions is a serious problem in many branches
of industry, such as electroplating, mining, paint and coatings, fertilizer and
electrochemical. Increasing environmental awareness, government regulations
and pollution fees for discharging hazardous wastes require the business to
improve the utilization of the produced wastes. Biomaterials are researched
extensively for their ability of heavy metals removal. They can be a viable
alternative for physiochemical methods, especially at heavy metal
concentrations below 100 mg/dm3. As biosorbents various byproducts or
wastes of biological origin may be used. The main advantages of such materials
are availability, high efficiency and low cost (1-7). Our previous studies
presented pectin-based and new hybrid pectin-guar gum biosorbents (8).
Although guar gum addition did not change adsorption properties significantly,
but influenced on adsorption kinetics by enhancement the swelling of beads.
The aim of this work was to prepare pectin-based biosorbents containing other
polysaccharides of natural origin (gellan gum, carob bean gum, xanthan gum)
and investigate their properties.
The aqueous solutions of polysaccharides (pectin with other polysaccharide)
were dropped into cold calcium chloride solution (1M) employing peristaltic
pump. Biosorbents were left for 24 h in laboratory fridge (4°C). Next, after
filtration, obtained beads were washed for complete removal of chloride ions
and were dried in 40°C.
Our studies showed that maximal possible amount of studied gums immobilized
in pectin biosorbent, differed for various polysaccharides. Physicochemical and
sorption (Cd, Pb) properties of obtained biosorbents of various composition
were also investigated.
Acknowledgements: This work was financed by Polish Ministry of Science and Higher
Education as „Iuventus Plus” grant No IP2014 016173 (2015-2017).
References
1. F.A. Pavan et al., Biochem. Eng. J., 40 (2008) 357-362.
2. J.T. Matheickal, O. Yu, Bioresour. Technol., 69 (1999) 223-229.
3. N. Barka, M. Abdennouri, A. Boussaoud, M.El. Makhfouk, Desalination, 258 (2010) 66-71.
4. L. Sha et al., Trans. Nonferr. Metal. Soc., 20 (2010) 187-191.
5. R.P. de Carvalho, K.H. Chong, B. Volesky, Biotechnol. Progr., 11 (1995) 39-44.
6. Y.N. Mata et al., Chem. Eng. J., 150 (2009) 289-301.
7. Y.N. Mata et al., J. Hazard. Mater., 178 (2010) 243-248.
8. A. Jakóbik-Kolon, A.K. Milewski, K. Mitko, A. Lis, Sep. Sci. Technol., 49 (2014) 1679-1688.
87
HYDROGELS APPLICATION IN HEAVY METAL COMPLEXES
REMOVAL
Dorota Kołodyńska1, Alicja Skiba2, Zbigniew Hubicki1
1
Department of Inorganic Chemistry, Faculty of Chemistry, Maria Curie
Skłodowska University, 20-031 Lublin, Poland,
2 New Chemical Synthesis Institute, Al. Tysiąclecia Państwa Polskiego 13a, 24110 Puławy, Poland
e-mail: kolodyn@poczta.onet.pl
Polymer superabsorbents (PSA) commonly known as hydrogels are crosslinked highly molecular compounds able to absorb water from physicochemical
fluids in the amounts from tenfold to one hundredfold larger than their dry mass.
The most desirable features of hydrogels as regards their application are first of
all: large adsorption capacity, high rate of reversible fluid absorbing power,
mechanical strength, non-toxicity, chemical resistance as well as mechanical
resistance (particularly essential in special application of hydrogels) and water
absorbing ability in the saline solution. The above mentioned materials are
widely applied in many fields of industry. They are used, among others, in
medicine, agriculture, pharmacy, cosmetics, electronics, gardening, forestry,
architecture as well as in many branches of chemical industry (1-3).
In the presented paper the commercial hydrogel TerraHydrogel®Aqua was
used for the adsorption of Cu(II), Zn(II), Mn(II) and Fe(III) complexes with IDS. It
is also available as Baypure CX 100 (Laxness, Germany). (N-1,2dicarboxyethyl)-D,L-aspartate acid, also known as iminodisuccinic acid, belongs
to the group of the biodegradable complexing agents of a new generation. It is
an environmentally friendly and non-toxic. After the effective adsorption of the
above mentioned complexes with a biodegradable complexing agent
preparation of slow-release fertilizers of controlled activity of a new generation
is possible. It should be mentioned that only a few producers offer this type of
commercial fertilizers.
It was found that the adsorption process of Cu(II), Zn(II), Mn(II) and Fe(III)
complexes with IDS onto THA proceeds according to the pseudo second order
mechanism reaction, as evidenced by high values of the determination
coefficients. The process efficiency increases with the increasing phase contact
time. The adsorption mechanism can be described by the Langmuir equation.
The process is also temperature dependent. As follows from the experiments
the presence of chloride ions adversely affects the process efficiency.
References
1. E.M. Ahmed, J. Adv. Res., 6 (2015) 105-121.
2. H.F. Sun, B. Liu, Z. Jing, H. Wang, Carbohydr. Polym., 118 (2015) 16-23.
3. F.L. Buchholz, A.T. Graham, Modern Superabsorbent Polymer Technology, Wiley–VCH,
New York 1998.
88
REMOVAL OF GLDA COMPLEXES WITH HEAVY METALS
ON N-METHYL-D-GLUCAMINE RESIN
Dorota Kołodyńska, Irmina Pańczuk-Figura, Zbigniew Hubicki
Department of Inorganic Chemistry, Faculty of Chemistry, Maria Curie
Skłodowska University, 20-031 Lublin, Poland
e-mail: kolodyn@poczta.onet.pl
GLDA is a non-toxic, biodegradable complexing agent of a new generation.
Synthesis of GLDA is based on the fermentation flavour enhancer monosodium glutamate, corn molasses. It should be mentioned that low toxicity
(LD50 > 2000 mg / kg) makes that GLDA safe for humans. In comparison with
phosphates it does not contribute to eutrophication and as a component of
various types of detergents, it removes stains better than overs based on
traditional complexones. It possesses many advantages such as shown in the
scheme below:
In the paper the kinetic and adsorption studies of heavy metal complexes with
GLDA removal from aqueous solutions using the ion exchangers with the Nmethyl-D-glucamine functional groups ―CH2-N(CH3)-CH2-C6H8(OH)5 are
presented. They exhibit high selectivity towards boron in the form of trioxoboric
acid (1-3). Therefore they should be also characterized by the affinity for anionic
complexes of Pb(II), Cd(II) as well as Cu(II) and Zn(II) with GLDA. Different
parameters affected the sorption kinetics and equilibrium studies during static
and dynamic tests. It was found that the determined sorption efficiencies of the
tested resins with respect to the above mentioned complexes with GLDA
depends on the contact time and the concentration of the working solution and
accompanying Cl- and SO42- ions.
References
1. F. Soto, E.M. Camacho, Desalination, 181 (2005) 207-216.
2. B.F. Urbano, B.L. Rivas, F. Martinez, S.D. Alexandratos, React. Funct. Polym., 72 (2012)
642-649.
3. N. Kabay et al., Desalination, 223 (2008) 49-56.
89
TRANSPORT OF GOLD ACROSS POLYMER INCLUSION
MEMBRANES CONTAINING
N-(DIETHYLTHIOPHOSPHORYL)-AZA[18]CROWN-6
Marta Kołodziejska1, Cezary Kozłowski2, Jolanta Kozłowska2
1
Department of Metal Extraction and Recirculation, Częstochowa University
of Technology, 42-200, Częstochowa, Armii Krajowej 19, Poland,
2 Institute of Chemistry, Environment Protection and Biotechnology,
Jan Długosz University of Częstochowa, 42-201 Częstochowa,
Armii Krajowej 13, Poland
mail: martakolodziejska@wip.pcz.pl
This work presents the synthesis of functionalized monaza crown ether i.e. N(diethylthiophosphoryl)-aza[18]crown-6 and its application as the ion carrier in
competitive transport of Au(III) across polymer inclusion membranes. The
synthesis of thiophosphorylated aza[18]crown-6 was performed with good yield.
The polymer inclusion membranes (PIMs) with this lariat have been
successfully developed for selective transport of Au(III) from chloride aqueous
solution as feed phase into various receiving phases. For PIMs used in
transport the optimal content was as follows: 20 wt.% of cellulose triacetate as
the support, 15 wt.% of the ionic carrier, and 65 wt.% of o-nitrophenyl pentyl
ether as the plasticizer.
O
O
O
O
S
(EtO)2P(S)Cl
O
O
HN
O
O
aza[18]crown-6
Et3N / CHCl3
N
P
OE t
OE t
O
O
N-(diethylthiophosphoryl)-aza[18]crown-6
The lariat ether, i.e. N-(diethylthiophosphoryl)-aza[18]crown-6 was studied to be
applied in the carrier-facilitated transport of gold(III) (chloride media) across a
PIM. The presence of chloride salts in the aqueous media improves the
transport. In chloride media, the carrier is able to transport gold(III), decreasing
the permeability as the initial HCl concentration is increased. At 0.25 mol·dm-3
concentration of N-(diethylthiophosphoryl)-aza[18]crown-6 (based on plasticizer
and carrier) the ion carrier causes that the polymer inclusion membrane is
saturated and the transport rate is maximal; the fluxes for Au(III) were 5.1
µmol/m2s.
The stripping agent in the receiving phase plays an important role in removal of
metal ions from the membrane phase. The influence of different stripping
agents in the receiving phase on the transport of Au(III) using N(diethylthiophosphoryl)-aza[18]crown-6 was also studied. The experiments were
carried out for different types of stripping agents, i.e. hydrochloric acid,
potassium iodide or thiourea in the concentration range of 0.1-0.5 mol·dm-3.
Acknowledgments: This work is part of the project The authors acknowledge Polish National
Science Centre for financial support of this project.
90
RESORCINARENES AS ION CARRIERS OF Au(III), Pt(IV), Pd(II)
IN TRANSPORT ACROSS IMMOBILIZED MEMBRANES
Marta Kołodziejska2, Cezary Kozłowski1, Jolanta Kozłowska1, Iwona
Zawierucha1
1 Institute of Chemistry, Environment Protection and Biotechnology, Jan
Długosz University of Częstochowa, 42-201 Częstochowa, Armii Krajowej 13,
Poland,
2 Department of Metal Extraction and Recirculation, Częstochowa University of
Technology, 42-200, Częstochowa, Armii Krajowej 19, Poland
e-mail: c.kozlowski@ajd.czest
This work presents the synthesis of functionalized rezorcinarenes and
application of them as the ion carriers in competitive transport of Au(III), Pt(IV),
Pd(II) across polymer inclusion membranes. The synthesis of ion carriers 1 and
2 were performed with good yield. The polymer inclusion membranes (PIMs)
with resorcinarenes 1 and 2 have been successfully developed for selective
transport of Au(III), Pt(IV), Pd(IV) from chloride aqueous solution as feed phase
into various receiving phases. The optimal PIM content was as follows: 20 wt.%
of cellulose triacetate as the support, 15 wt.% of the ionic carrier, and 65 wt.%
of o-nitrophenyl pentyl ether as the plasticizer.
H3C
OH
CH3
CH3
OH
N
N
H3C
O
O
O
CH3
HO
OH
O
OH
HO
H3C
HO
HO
OH
OH
HO
OH
HO
HO
OH
OH
HO
OH
H3C
OH
OH
HO
CH3
O
O
OH
O
H3C
N
OH
O
N
HO
CH3
1
H3C
CH3
2
The resorcinarenes 1 and 2 used as ion carriers for competitive transport of
gold(III), platinum(IV) and palladium(II) give preferential selectivity order: of
Au(III) > Pt(IV) > Pd(II), with high recovery for higher HCl concentrations of
aqueous solution. The following parameters influencing the transport of Au(III),
Pt(IV), Pd(II) were investigated i.e. types of extractants, types of stripping
agents as well as types of plasticizers (diluents). A reported model describing
the transport mechanism consists of: diffusion process through the feed
aqueous diffusion layer, fast interfacial chemical reaction and diffusion through
the membrane. At 0.25 mol·dm-3 concentration of resorcinarenes 1 and 2
(based on plasticizer and carrier) the polymer inclusion membrane saturation
was achieved. Under the optimal operating conditions Au(III) was successfully
separated from Pt(IV) and Pd(II); extraction efficiencies of Au(III) for
resorcinarenes 1 and 2 were 95% and 88%, respectively.
The stripping agent in the receiving phase plays an important role in removal of
metal ions from the membrane phase. The influence of different stripping
agents in the receiving phase on the transport of Au(III), Pt(IV) and Pd(II) using
resorcinarenes 1 and 2 was also studied. The experiments were carried out for
different types of stripping agents, i.e. potassium iodide, sodium thiosulfate or
EDTA in the concentration of 0.01 mol·dm-3.
Acknowledgments: This work is part of the project no. 2011/01/D/ST5/05781. The authors
acknowledge Polish National Science Centre for financial support of this project.
91
MOLECULARLY IMPRINTED POLYMERIC ADSORBENT FOR
β-BLOCKERS REMOVAL SYNTHESIZED USING
FUNCTIONALIZED MSU-F SILICA AS A SACRIFICIAL
TEMPLATE
Małgorzata Kujawska, Andrzej W. Trochimczuk
Faculty of Chemistry, Wrocław University of Technology,
Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland
e-mail: malgorzata.kujawska@pwr.edu.pl
The growing demand for more and more sensitive analytical techniques
resulted in development of improved technologies, including application of
molecularly imprinted polymers as a selective adsorbents in solid-phase
extraction, sensors and membranes.
In this work preparation of polymeric adsorbent using novel method combining
synthesis of molecularly imprinted polymers and hard template technique is
presented. First, MSU-F structured silica was modified (Figure 1) and used as a
template during bulk polymerization of methacrylic acid and ethylene glycol
dimethacrylate. Later, prepared polymer was purified, ground and sieved.
Finally, silica was removed using acidic ammonium fluoride, whereas resulting
polymer was washed in ion-exchange column. Material was characterized for
the content of carboxylic groups, swelling properties and capability of metoprolol
adsorption. Porous structure of material was studied using nitrogen adsorption
at liquid nitrogen temperature and scanning electron microscopy. Results
confirmed that use of structured silica allows to design the polymer porous
structure. Moreover, sorption studies of β-blockers proved obtaining material
with cavities complementary to modified silica template.
Fig. 1. Modification of silica
Due to the presence of active sides and designed porous structure, polymer
material prepared using modified silica template, after further studies, could be
applied as useful sorbent for selective extraction of pharmaceuticals.
References
1. C. Baggiani et al., J. Chromatogr. A, 1218 (2011) 1828-34.
2. A. Fuertes et al., Microporous Mesoporous Mater., 112 (2008) 319-326.
92
MINE WATER NANOFILTRATION – SEPARATION OF MONO
AND POLYVALENT IONS
Ewa Laskowska, Krzysztof Mitko, Marian Turek
Silesian University of Technology, Faculty of Chemistry, ul. B. Krzywoustego 6,
44-100 Gliwice, Poland
e-mail: laskowska.ewi@gmail.com
Coal mining produces large amount of saline waters, which have to be desalted
before their discharge to the environment. Nanofiltration was proposed as a first
step of high-salinity coal mine water treatment (TDS ca. 54 g/dm3).
Nanofiltration experiments were performed using dead-end HP4750 Stirred Cell
(Osmonics, USA) with effective membrane area 14.6 cm2 temperature 21°C.
High stirring speed (1200 rpm) was applied to avoid concentration polarization.
Five types of membranes from different producers were examined: NF270 (Dow
Filmtec), NFX, NFG, NFW (Synder) and NFDL – 5 (Desal).
The dependences of Ca2+, Mg2+, Na+, SO42-, and Cl- ion rejection coefficients on
water recovery were determined for each of the tested membranes. The
maximum possible recovery rate allowing avoiding of sparingly soluble salts
crystallization on the membrane surface were found as follows: 92%, 89.9%,
86%, 91.5%, and 84.7% for NF270, NFX, NFG, NFW, and NFDL – 5,
respectively. Maximum sulphate rejection was over 95% (NFDL – 5 membrane),
while minimum rejection was less than 30% (NFG membrane). At the same
time maximum chloride rejection was 27% (NF270 membrane), while minimum
rejection was less than 5% (NFG membrane). NFDL – 5 membrane exhibits
maximum rejection values of Ca2+, Mg2+, Na+ cations (83%, 90%, 43%,
respectively) while negative rejection of Ca2+ and Mg2+ ions was observed on
NFG membrane. The studies confirmed the nanofiltration might be used as first
step of brine or salt production. Controlled crystallization of calcium sulphate
can be performed from the retentate.
Acknowledgements: Author received a grant of the "DoktoRIS project - scholarship program for
innovative Silesia" co-financed by the European Union of the European Social Fund.
.
93
SEPARATION OF WHEY COMPOUNDS IN PRESSURE
MEMBRANE PROCESSES: PROTOCOL FOR THE ORGANIC
COMPOUNDS FRACTIONATION TO THEIR FURTHER USE
Magdalena Lech, Anna Trusek-Holownia
Wrocław University of Technology, Faculty of Chemistry, Group of Bioprocess
and Biomedical Engineering, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław,
Poland
e-mail: magdalena.lech@pwr.edu
Post-production whey has a high concentration of proteins and lactose that has
to be decreased 500-fold before disposal in the environment. This paper
describes goat whey components separation using membrane techniques and
presents the ways to further use of the fractionated valuable compounds.
To decrease the natural turbidity of whey (due to residual casein clot and fat),
the whey was centrifuged, treated with CaCl2, heated to 55°C and finally
centrifuged again. Whey proteins are valuable and have health-promoting
properties; therefore, recovery of them is potentially economically feasible. For
this purpose, ceramic and polyethersulfone membranes with a cut-off coefficient
of 80-150 kDa have been tested. Working with the polymer membrane provided
a low degree of adsorption of proteins and a steady stream of permeate. That is
why the separation on this membrane at pH equal to 9.0 was chosen. By
including diafiltration with ultrafiltration, the glycomacropeptides, α-lactoalbumin
and β-lactoglobulin could be diluted completely and the most valuable whey
proteins (serum albumin and lactoferrin) concentrated in retentate.
Fractionation of the mixture of proteins present in whey can allow those with
special nutritional properties hydrolyse to shorter sequences better assimilated
by the body than the protein. Hydrolysates with great health benefits can be
obtained by enzymatic (controlled) hydrolysis of the individual compound and
then separated by nanofiltration. For this purpose, ceramic and polyethersulfone
membranes with a cut-off coefficient of 1-15 kDa under different conditions (pH,
ionic strength) have been tested. Selection of the membrane and the conditions
of separation should be based on the expected range of molecular weight
components in permeate.
Using polyethersulfone membrane with a cut-off coefficient of 1-3 kDa the
lactose retention was equal to 0.862. This retentate stream rich in lactose and
macropeptides was successfully biodegraded in a continuous stirred-tank
reactor with a B. licheniformis strain. The bacteria effectively decreased the
organic compounds content at co-production of lactic acid. Lactic acid is used
widely in the cosmetic and food industries, so this integrated approach yields
additional economic benefits.
After laboratory-scale testing, a concept for an industrial-scale process for the
fractionation and further utilization of the most valuable whey compounds was
elaborated.
94
FUNCTIONALIZED POLY(HIPE) AS A MONOLITH ADSORBENT
FOR ION EXCHANGE PROCESS
Magdalena Legan, Andrzej W. Trochimczuk
Faculty of Chemistry, Wroclaw University of Technology,
e-mail: magdalena.legan@pwr.edu.pl
Crosslinked polymers that possess the ability to exchange ions with a solution –
ion-exchangers are widely used in many areas, such as chemistry, analytical
chemistry as well as in technological processes such as water treatment,
wastewater purification, precious metal removal from hydrometallurgical
effluents etc. Therefore, in several research groups the investigations concern
the syntheses and applications of new and specific ion-exchange materials.
The aim of this work was to obtain and characterize the selectivity of new type
of ion-exchanger – porous, highly basic monolith with HIPE (High Internal
Phase Emulsion) structure (1,2). Hydrophobic monolith of (vinylbenzyl chloride)
/ (divinylbenzene) (VBC/DVB) with HIPE structure was prepared in the water in
oil (w/o) emulsion. The resulting polymer with HIPE structure was modified
using N-methylimidazole and N-butylimidazole under conditions allowing for the
preservation of porous structure (Fig. 1). Porous structure after polymerization
and after the modification was checked using Scanning Electron Microscopy.
Ion-exchange ability and selectivity of monolithic anion-exchanger was tested
towards the following inorganic anions: F-, Cl-, NO3-, SO42- Mo7O246-, PO43- as
well as selected organic anions. Sorption of anions was done from single and
multicomponent solutions. As the measure of sorption effectiveness, the
maximal sorption capacity taken from the appropriate sorption isotherms and
the selectivity coefficients calculated from partition coefficients were used. The
concentration of anions before and after sorption was measured using ionchromatography. New, hydrophilic and highly porous monolithic material
presented in this work, can be used in ion chromatography, in analytical
chemistry for the preconcentration of anions before analysis, in selective
sorption of some ions such as molibdate from the tailings and
hydrometallurgical effluents.
Fig. 1. Structure of functionalized poly(HIPE)
References
1. S.D. Kimmins, N.R. Cameron, Adv. Funct. Mater., 21 (2011) 211-225.
2. Y. Chang, H. Liu, F. Zha, H. Chen, X. Ren, Z. Lei, Chem. Eng. J., 167 (2011) 183-189.
95
COMPETITIVE TRANSPORT OF Fe(III) AND Mn(II) IONS
THROUGH BULK LIQUID MEMBRANES
C. M. Mirea, I. Diaconu, E. A. Serban, E. Ruse, G. Nechifor
University Politehnica Bucharest, Faculty of Applied Chemistry and Materials
Science, Department of Analytical Chemistry and Environmental Engineering,
no 1-7 Polizu Street 7000 Bucharest
e-mail: diaconuioana12@yahoo.com
In the present paper the competitive transport of Fe(III) and Mn(II) ions from 12.5 mol/L solutions of HCl in the presence of Aliquat 336 was studied. The
transport experiments were realised in a wall in wall type of cell using as
membrane solvent CHCl3 in which the carrier Aliquat 336 was dissolved at a
concentration of 10-2 mol/L.
Transport parameters such as: concentration of Fe(III) and Mn(II) ions in the
feed phase in the concentration range of 10-4 – 10-3 mol/L and 10-5 – 10-4 mol/L,
respectively, HCl concentration in the stripping phase in the range 10-3 – 10-1
mol/L and the transport time were studied.
For both cations the efficiency of the process increases with the increase of the
HCl concentration in the feed phase. Transport efficiencies of over 90% were
obtained when the HCl concentration in the feed phase is higher than 2 mol/L,
using an 18 hours transport time. The transport mechanism was correlated with
the formation of chemical species such as MnClx2-x (x=1-6) and FeCly3-y (y = 14), respectively formed by the two cations in the presence of HCl. These
chemical species form a complex with the carrier at the interface feed phase|
membrane, crosses through the chloroform membrane that contains the carrier
and decomposes at the interface membrane|stripping phase.
Acknowledgements: The work has been funded by the Sectoral Operational Programme Human
Resources Development 2007-2013 of the Ministry of European Funds through the Financial
Agreement POSDRU/159/1.5/S/134398.
References
1. B. Pospiech et al., Physicochem. Probl. Miner. Process., 44 (2010) 195-204.
2. R.K. Mishra et al., Hydrometallurgy, 108 (2011) 93-99.
96
SELECTIVE RECOVERY OF Dy FROM WASTE Nd MAGNET
USING COATED SOLVENT IMPREGNATED RESIN
Hironori Murakami, Syouhei Nishihama, Kazuharu Yoshizuka
e-mail: v4maa020@eng.kitakyu-u.ac.jp
1. Introduction
Rare earth magnet is widely used for motors in electric vehicles, compressors,
and so on, and a lot of magnets are currently disposed. Dysprosium (Dy) is
included in Neodymium (Nd) magnet for enhancing the coercive force of Nd
magnet. Since Dy is however distributed in limited countries, stable supply of Dy
is required. In the present work, separation of Dy from waste Nd magnet was
investigated using a solvent impregnated resin (SIR) containing 2ethylhexylphosphonic acid mono-2-ethylhexyl ester (PC-88A), coated by
polyvinyl alcohol (PVA) crosslinked by glutaraldehyde (GA).
2. Experimental
SIR was prepared by conventional procedure using HP2MG as a support, and
then the SIR was coated by PVA crosslinked by GA. Batchwise adsorption was
carried out by shaking 20 mL of aqueous solution ([Dy] = [Nd] = 1.0 mmol/L)
and 0.02 g of SIR for 24 h. Column adsorption was carried out by feeding the
aqueous solution ([Dy] = 1.0 mmol/L, [Nd] = 5.0 mmol/L) to the column packed
with SIR. The metals loaded were eluted with 1.0 mol/L HNO3. Concentrations
of metals were determined by ICP-AES.
CM [mmol/L]
CM [mmol/L]
In the batchwise adsorption, adsorption of Dy was higher than that of Nd.
Separation of Dy was achieved at pH < 2.00, where almost no adsorption of Nd
was occurred. Therefore, separation of Dy and Nd with column adsorption was
investigated by using feed solution of pH < 2.00. Figure 1 shows adsorption and
elution curves of the two metals using feed solution of pH = 1.50. Dy and Nd
were started to be broken through at B.V. ≈ 100 and B.V. ≈ 30, respectively. In
addition displacement of Nd adsorbed and Dy in the aqueous solution was
progressed at B.V. = 50 – 400. Quantitative elution of Dy was achieved by 1.0
mol/L HNO3. When pH of the feed solution was changed as 2.00, 1.90, 1.80
and 1.50, purity of Dy in
7
35
the
eluent
were
6
30
increased as 85.8 %,
5
25
90.9 %, 93.6 % and
4
20
95.8%, respectively. This
Dy
3
15
is due to the inhibition of
Dy
Nd
2
Nd
10
Nd
adsorption
by
decreasing pH. More
1
5
effective separation of
0
0
0 100 200 300 400 500 600
0
10
20
30
40
50
the metals is expected to
B.V. [-]
B.V. [-]
be
achieved
by
Fig. 1. Breakthrough and elution curves of Dy and Nd
optimizing pH of the feed
with the coated SIR
solution.
97
SELECTIVE TRANSPORT OF Ag(I) AND Cu(II) ACROSS
PLASTICIZED MEMBRANES WITH CALIX[4]PYRROLES
Anna Nowik-Zając1, Cezary Kozłowski1, Andrzej Trochimczuk2
1 Institute
of Chemistry, Environment Protection and Biotechnology, Jan
Dlugosz University of Czestochowa, 42-201 Czestochowa, Armii Krajowej
13/15, Poland
2 Faculty of Chemistry, Wroclaw University of Technology, 50-370 Wroclaw,
Poland
e-mail: a.zajac@ajd.czest.pl
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 polymeric 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
0.0005 mol/dm3 AgNO3 and Cu(NO3)2; 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. We found that the
transport of Ag(I) and Cu(II) across PIM with 1 and 2 via carrier mediated
mechanism depended on pH driving force processes. The competitive transport
of Ag(I) and Cu(II) from aqueous phases across PIM is an effective separation
method for silver(I) ions.
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, H.C. Mandalia, H.S. Gupte, D.J. Vyas, 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.W. Trochimczuk, Desalination, 294 (2012) 25-29.
98
REMOVAL OF HEAVY METAL IONS THROUGH ION EXCHANGE
Cristina Orbeci1, Cristina Modrogan1, Alexandra Raluca Miron1,
Firas Hashim Kamar2
1 University
2 Institute
Politehnica of Bucharest, Street Polizu, nr.1-7, Bucharest, Romania,
of Technology-Baghdad, Foundation of Technical Educations, Iraq
e-mail: cristina27ccc@yahoo.com
The last decades have shown a reevaluation of the issue of environmental
pollution, under all aspects, both at regional and international level. Therefore, it
is necessary to remove the pollutants before discharging them into the
environment. Different methods can be used to remove heavy metals, including
filtration, chemical precipitation, coagulation, solvent extraction, electrolysis, ion
exchange, membrane process and adsorption (1-4). Ion exchange is a common
and effective process. It is particularly used in the purification of drinking water
and in the removal of hazardous substances - industrial effluents, which are
present even in very low concentrations in the chemical industries (5). The most
frequent heavy metals are chromium, cobalt, nickel, copper, zinc, arsenic,
selenium, silver, cadmium, antimony, mercury, thallium and lead. The removal
of heavy metal ions from various types of water and wastewaters is an essential
issue in environmental protection with an important result for human health.
Cadmium is a toxic heavy metal present in wastewaters from a variety of
industries.
In this paper, the cadmium adsorption by the Purolite MN 200 and Purolite MN
400 ion exchangers was investigated in equilibrium conditions and in dynamic
systems at 20°C. The separation factors, obtained from the equilibrium data,
were very similar to the isotherms Cd-MN 200 and Cd-MN 400, which indicates
that, in equilibrium conditions, both ion exchange resins remove similar
quantities of cadmium ions. The dynamic data were used to estimate some
parameters, such as mass transfer zone length; time of formation of the mass
transfer zone; time evolution of the mass transfer zone; the use of ion exchange
until break time. Moreover, through the dynamic capacity of the column, it was
concluded that the Purolite MN 200 had been more efficient, in dynamic
conditions, for the removal of cadmium.
Agreement POSDRU/159/1.5/S/134398.
References
1. M. Anis, S. Haydar, A.J. Bari, Environ. Eng. Manag. J., 12(11) (2013) 2117-2124.
2. A.C. Basha et al., Chem. Eng. J., 171 (2011) 563-571.
3. C. Bohdana, D.S. Cantea, J.A. Dale, E. Pincovschi, A.M.S. Oancea, Proceedings IEX,
Cambridge, 2008, 427-434.
4. G. Crini, N. Morin-Crini, N. Fatin-Rouge, S. Déon, P. Fievet, Arab. J. Chem., 2014,
doi:10.1016/j.arabjc.2014.05.020.
5. Y. Bai, B. Bartkiewicz, Pol. J. Environ. Stud., 18(6) (2009) 1191-1195.
99
STRUCTURAL AND FUNCTIONAL CHARACTERIZATION OF
MEMBRANE PROCESSES, THROUGH SPECIFIC TECHNIQUES
AND MATHEMATICAL MODELS
Daniela-E. Pascu1, Alexandra R. Miron1, Mihaela Pascu (Neagu)2,
Aurelia C. Nechifor1, Bogdan I. Bita3,4, Marian C. Popescu3,5,
Cornel Trisca-Rusu1,3, Eugenia Eftimie Totu1
1 Faculty
of Applied Chemistry and Materials Sciences, Politehnica University of
Bucharest, Gheorghe Polizu Street, No.1-7, Bucharest, 011061, Romania,
2 SC HOFIGAL S.A. Analytical Research Department, 2 Intr. Serelor, Bucharest4, 042124, Romania,
3 National Institute for R&D in Microtechnologies, 126A Erou Iancu Nicolae
street, 023573, Bucharest, Romania,
4 Faculty of Physics, University of Bucharest, 405 Atomistilor street, 077125,
Magurele, Romania,
5 Faculty of Electronics, Telecommunications and Information Technology,
University “Politehnica” of Bucharest, 1-3 Iuliu Maniu Blvd., 061071, Bucharest,
Romania
e-mail: dpascu@yahoo.com
The aim of this study was to characterize the composite membranes by two
methods: direct (SEM and FT-IR) and collateral, performed using various
optimization programs / mathematical modelling.
The membranes have been prepared by polysulfone’s coagulation method from
aniline by phase inversion and morphologically characterized using electronic
microscopy scanning (SEM), and also by using the MathCAD program.
Membranes show sizes ranging from 1-100 μm. The membranes were used for
biologically active principles concentration in some herbal medicines.
Biologically active principles were highlighted by two polyphenols dosing
methods. The use of mathematical modelling program revealed the transport
and adsorption of biologically active substances through composite
membranes. The transport systems have been successfully used to control the
release of active substance report, to obtain a retard action of the active
substance and to direct the drug to the targeted organ.
Here is presented an easy way for determining the optimum parameters needed
for the calculation of composite membrane specific adsorption capacity, which
has been experimentally achieved. The main purpose of this work was to
develop a series of mathematical models in order to describe the relationship
between: biologically active substances adsorption membranes capacity, initial
concentration and time, and also to characterize the composite membrane.
Acknowledgements: The work has been funded by the Sectorial Operational Programme
Human Resources Development 2007-2013 of the Ministry of European Funds through the
Financial Agreement POSDRU/159/1.5/S/132395, POSDRU/159/1.5/S/134398. Faculty of
Applied Chemistry and Materials Sciences, Politehnica University of Bucharest, support is also
gratefully acknowledged.
References
1. M. Pascu et al., J. Iran. Chem. Soc., 11 (2013) 315-321.
100
COMPOSITE MEMBRANES FOR THE PROCESSING OF
BIOLOGICALLY ACTIVE EXTRACTS
Mihaela Pascu (Neagu)1,2, Daniela-E. Pascu2, Andreea Cozea1,3,
Gina A. Traistaru4, Alexandra R. Miron2, Andrei A. Bunaciu5,
Cristina A. Nechifor2
1 SC
HOFIGAL S.A. Analytical Research Department, 2 Intr. Serelor, Bucharest4, 042124, Romania,
2 Politehnica University of Bucharest, Faculty of Applied Chemistry and Material
Science; 1-5 Polizu St, 11061 Bucharest, Romania,
3 Transilvania University of Brasov, Faculty of Food and Tourism Brasov, Castle
street, no. 148, 500036 Brasov, Romania,
4 S.C. ENECO Consulting S.R.L, sos. Pantelimon, 247, sector 2, Bucharest,
Romania,
5 SCIENT- Research Center for Instrumental Analysis, (S.C.
CROMATEC_PLUS S.R.L.), 18 Sos. Cotroceni, Bucharest, 060114, Romania
e-mail: dpascu@yahoo.com
The objective of this study was to obtain a pharmaceutical formulation involved
in stimulation of the cardiovascular system. This pharmaceutical product was
obtained by combining four concentrated fruit extracts: hawthorn
(Crataegusmonogyna), black mountain ash (Aronamelanocarpa), bilberry
(Vacciniummyrtillus L) and rose hip (Rosa canina). The active substances
(flavonoids) of medicinal plant species studied (fruits) are characterized by the
chemical structure, biological and pharmacodynamics actions thereof.
Composite membranes for processing biologically active extracts addresses
topical themes of science and technology with direct applications in membrane
biochemistry, biotechnology and biomedicine. Using composite membrane
separation processes (polysulfone), is isolating and purifying natural substances
of vegetable raw materials, both processes with high selectivity and low
environmental impact, which is an extremely interesting alternative to
conventional chemical models and mathematical models (ANN). The
pharmaceutical formula obtained from the four concentrated extracts was
analysed structural, morphological and compositional through various
techniques: IR, SEM, UV-VIS spectroscopy, liquid chromatography (HPLC).
The pharmaceutical product was developed at laboratory level on more
technological options being gradually tested by various enzymatic methods. For
the analysis of the major natural compounds of formula we have developed
appropriate analytical methods adapted to the new product preparation which
can be administered as adjuvant in the treatment of cardiovascular diseases.
Agreement POSDRU/159/1.5/S/132395 and POSDRU/159/1.5/S/134398. This paper is
supported by the Sectoral Operational Programme Human Resources Development (SOP
HRD), financed from the European Social Fund and by the Romanian Government under the
project number POSDRU/159/1.5/S/134378.
References
1. Ş.I. Voicu et al., Rom. J. Inf. Sci. Tech., 12(3) (2009) 410-422.
2. C. Modrogan et al., Rev. Chim. (Bucharest), 62(3) (2011) 272-277.
101
SYNTHESIS AND PHYSICO-CHEMICAL PROPERTIES OF GMA
TERPOLYMERS FOR ENZYMES IMMOBILIZATION
Beata Podkościelna
Department of Polymer Chemistry, Maria Curie-Skłodowska University, M.
Curie-Skłodowska sq. 5, 20-031 Lublin, Poland
e-mail: beatapod@umcs.pl
The microspheres for immobilization process must meet some requirements,
such as: particle size, surface properties and functionality. For this reason, in
their preparation, the use of monomers with reactive functional groups is highly
desirable. In recent years, copolymers based on glycidyl methacrylate (GMA)
have attracted increasing interest. (1-4) These compounds have in their
structure not only double vinyl bonds, but also very attractive epoxy groups.
These groups easily reacts with e.g. thiol or amino groups present in the
biological active compounds such as enzymes or proteins. Therefore, they can
be successfully applied to the most efficient covalent immobilization process.
Rigid, porous poly(divinylbenzene-glycidyl methacrylate-amide derivatives)
microspheres
were
synthesized
through
the
suspension-emulsion
polymerization with a mixture of toluene and decan-1-ol as the porogen (Fig. 1).
In this polymerization GMA and divinylbenzene (DVB) were used with different
amide derivatives: acrylamide (AA), methacrylamide (MA) or N,N’methylenebisacrylamide (MBAA). Glicydyl methacrylate introduced epoxy
functionalization in the obtained terpolymers. Physico-chemical properties
(porous structure, swellability, thermal properties, elemental composition) of the
new obtained enzyme carriers were investigated.
DVB-GMA-MA
DVB-GMA-AA
DVB-GMA- MBAA
Fig. 1. Photos of GMA terpolymers
References
1. R. Prodanović, S. Jovanović, Z. Vujčić, Biotechnol. Lett., 23 (2001) 1171-74.
2. A. Onjia, S.K. Milonjić, N.N. Jovanović, React. Funct. Polym., 43 (2000) 269-277.
3. B. Podkościelna, J. Appl. Polym. Sci., 120 (2011) 3020-3026.
4. M. Trytek, J. Fiedurek, B. Podkościelna, B. Gawdzik, M. Skowronek, J. Ind. Microbiol.
Biotechnol., doi:10.1007/s10295-015-1619-4.
102
SYNTHESIS, STRUCTURE AND PROPERTIES OF THE NEW
MICROSPHERES WITH LIGNIN UNITS
Beata Podkościelna, Andrzej Bartnicki, Barbara Gawdzik
Department of Polymer Chemistry, Maria Curie-Skłodowska University, M.
Curie-Skłodowska sq. 5, 20-031 Lublin, Poland
e-mail: beatapod@umcs.pl
Lignin is one (next to cellulose and hemicellulose) of the basic components of
the wood. The content of lignin in the wood is from 15 to 36 %. It gives the wood
compressive strength and rigidity. Lignin is a biopolymer and the main
renewable source of aromatic structures in Nature. On an industrial scale is
obtained as waste product during paper production (1).
Due to the presence of different functional groups, (e.g. –OCH3, -OH, -SH) in
lignin structure, its chemical modification is very prospective. Therefore, the
reaction between lignin hydroxyl groups and acrylic acid was carried out. In this
way, vinyl groups capable of polymerization reaction have been introduced (2).
Next, suspension-emulsion polymerization of styrene (St), 1,1’-bis[4-(2-hydroxy3-acryloiloxypropoxy)phenyl]cyclohexane (AC) and lignin unmodified form (L) or
lignin modified with acrylic acid (LA) was performed (Fig. 1). Due to the
presence of pore forming diluents, the reaction product had the form of porous
microspheres. Their chemical structures of all new compounds were confirmed
by ATR-FTIR analysis. The thermal stability and degradation behaviour of the
new materials were investigated. Additionally, the porous structure of the
microspheres in dry state from nitrogen adsorption-desorption measurements
was studied.
Fig. 1. Chemical structure of monomers
Acknowledgements: 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 n° PIRSES-GA-2013-612484.
Reference
1. A. Duval, M. Lawoko, React. Funct. Polym., 85 (2014) 79-96.
2. B. Podkościelna, M. Sobiesiak, Y. Zhao, B. Gawdzik, O. Sevastyanova, Holzforschung, DOI:
10.1515/hf-2014-0265.
103
HYDROPHOBIC AGGREGATION OF FINE CALCIUM
CARBONATE PARTICLES IN AQUEOUS SOLUTION
Izabela Polowczyk, Anna Bastrzyk, Tomasz Koźlecki
Chemical Engineering , Norwida 4/6, 50-373 Wrocław, Poland
e-mail: izabela.polowczyk@pwr.edu.pl
The aim of this work was to investigate the effect of surfactants adsorption on
the behaviour of fine calcium carbonate particles in suspensions.
The stability of precipitated calcium carbonate suspensions in the presence of a
dodecylammonium hydrochloride (DDAHCl) and sodium dodecyl sulphate has
been studied through the measurements of light transmitted and scattered by a
sample in time. The destabilization kinetics profile was determined and the
instability index (TSI) was calculated for each sample using a Turbiscan
apparatus and respective software. The changes of a particle size distribution
(PSD) as a result of surfactant addition were monitored using a Mastersizer
2000 laser diffractometer. The intensity of mixing as well as ultrasound
application during the size distribution measurements were important factors
and provided information about the strength of agglomerates. The fractal
dimensions of agglomerates formed in the presence of surfactant were
calculated. In addition, the adsorption isotherms of both surfactants were
determined and zeta potential measurements were carried out. The structure of
calcium carbonate agglomerates was also investigated using an optical
microscope.
The experimental results showed that DDAHCl can induce stronger aggregation
of fine calcium carbonate particles in suspension than SDS. Moreover, the
mechanism of adsorption of these surfactants is different. The instability index
increased slightly in the presence of anionic surfactant. In addition, the particle
size distribution analyses confirmed weaker agglomerate formation. On the
other hand, the presence of cationic surfactant resulted in the close-packed
agglomerates. The TSI increased significantly with increasing concentration of
DDAHCl up to some point and dramatically fell below the value obtained for
surfactant-free sample. Based on an analysis of PSD and microscopic images,
the contribution of fine particles among agglomerates increased. The
explanation of this could be the adsorption isotherm, which showed two regions,
which might correspond to a hemi-micelle and admicelles of surfactant
molecules and promotes new particle stabilization in the suspension (1,2).
Acknowledgements: This work was financially supported by a statutory activity subsidy from the
Polish Ministry of Science and Higher Education for the Faculty of Chemistry of Wrocław
University of Technology.
References
1. Y.-Q. Ji et al., Colloids Surf. A, 298 (2007) 235-244.
2. Y. Hu et al., Colloids Surf. A, 434 (2010) 281-286.
104
INFLUENCE OF pH ON ARSENIC(III) REMOVAL BY FLY ASH
Justyna Ulatowska, Izabela Polowczyk, Tomasz Koźlecki, Anna Bastrzyk,
Ewelina Szczałba, and Zygmunt Sadowski
Chemical Engineering , Norwida 4/6, 50-373 Wrocław, Poland
e-mail: izabela.polowczyk@pwr.edu.pl
In the world there are many regions where the concentration of arsenic in
drinking water is very high, e.g., Chile, Argentina, India, Bangladesh, China,
Taiwan, USA, Canada, Hungary, and Poland (1,2). Arsenic dissolved in water is
acutely toxic and can lead to a number of health problems. It causes cancer of
skin, lungs, bladder, liver, and kidney as well as pigmentation changes, skin
thickening, neurological disorders, loss of appetite and nausea (3). Adsorption
is a method frequently used for the water purification from arsenic (2).
Fly ash is a waste material generated from power plants. Although the chemical
composition of fly ash differs and depends on the type of material burnt as well
as method of combustion, this material was reported as a good sorbent of
heavy metals from water and wastewater (4).
In the present study, fly ash was used as adsorbent for removal of arsenic(III)
from aqueous solution. Fly ash was obtained from burning brown coal and
biomass from the power plant in Zgierz (Poland). The objective of this study
was to compare arsenic(III) removal at natural pH i.e., imposed by fly ash (pH
10.5), with that at high alkaline (pH 12.5). The effect of adsorbent dosage,
contact time and temperature was investigated.
The maximum static uptakes of arsenic(III) by fly ash at natural and high
alkaline pH were achieved for adsorbent-to-arsenic ratios of 20 g/L and were 14
mgAs(III)/gsorbent and 20 mgAs(III)/gsorbent, respectively. Adsorption data of
arsenic(III) adsorption onto fly ash were described using the Langmuir and
Freundlich models. The thermodynamic parameters of the adsorption process
were determined at 25°C, 35°C and 45°C. The calculated values revealed that
arsenic(III) adsorption is a spontaneous and endothermic process. The process
kinetics was evaluated by pseudo-first, pseudo-second order and parabolic
diffusion models. The pseudo-second order chemisorption model showed the
highest correlation with the experimental data (R2 = 0.999). Obtained results
confirmed that fly ash could be considered as a potential adsorbent for removal
of arsenic(III) ions in aqueous solution, at both natural and high alkaline pH.
Acknowledgements: This work was financially supported by a statutory activity subsidy from the
Polish Ministry of Science and Higher Education for the Faculty of Chemistry of Wrocław
University of Technology.
References
1. H. Guo et al., J. Hazard. Mater., 186 (2011) 1847-1854.
2. D. Mohan, C.U. Pittman, J. Hazard. Mater., 142 (2007) 1-53.
3. M.A. Malana et al., Chem. Eng. J., 172 (2011) 721-727.
4. J. Ulatowska et al., Pol. J. Chem. Tech., 16(1) (2013) 21-27.
105
EVALUATION OF Pd(II) TRANSPORT FROM AQUEOUS
CHLORIDE SOLUTIONS ACROSS POLYMER INCLUSION
MEMBRANES WITH IONIC LIQUIDS
Beata Pośpiech
Department of Chemistry, Częstochowa University of Technology, 42-200
Częstochowa, Armii Krajowej 19, Poland,
e-mail: b.pospiech@wip.pcz.pl
In this work the efficient transport of palladium(II) ions from aqueous chloride
solutions by transport through polymer inclusion membrane (PIM) with
phosphonium ionic liquids has been studied.
Recently, ionic liquids (ILs) were used as extractants as well as ion carriers of
metal ions due to their important physicochemical properties. Most of the ILs
are liquid at room temperature and usually exhibit negligible vapor pressure (1).
Cellulose triacetate membranes containing o-nitrophenyl octylether (ONPOE)
as a plasticizer and phosphonium ionic liquids as the ion carriers have been
prepared and applied for investigations.
Palladium is a precious metal, which is used in a wide range of applications, i.e.
electrical engineering, industrial catalysts, jewelry as well as for production of
corrosion-resistant materials (2,3). Recovery of important metals from various
secondary materials is very often carried out by leaching process by inorganic
acids (4,5). Transport across PIMs can be used for separation and recovery of
valuable metal ions from leach liquor. Selectivity of the polymer membranes
depends on the kind of the ion carrier. The quaternary phosphonium salts are
considered as the promising extracting agents for recovery of heavy metals (6),
particularly platinum group metals (PGMs) (7).
Cyphos IL 101 (trihexyl(tetradecyl)phosphonium chloride) or Cyphos IL 104
(trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate) have
been investigated as the ion carrier of Pd(II) ions from hydrochloric acid
solutions. The effect of various parameters on the transport kinetic and
the recovery factor of palladium(II) was studied, including concentration of the
ion carrier in the membrane, hydrochloric acid concentration in the source
phase and the kind of the receiving phase.
Acknowledgements: I thank Cytec Industries Inc. for providing me with free samples of Cyphos
IL 104.
References
1. B. Pospiech, Hydrometallurgy, 154 (2015) 88-94.
2. T. Sadyrbaeva, J. Membr. Sci., 272 (2006) 195-201.
3. B. Pośpiech, Physicochem. Probl. Min. Process., 51 (2015) 281-291.
4. A. Chagnes, B. Pośpiech, J. Chem. Technol. Biotechnol., 88 (2013) 1191–1199.
5. S. Genand-Pinaz, N. Papaiconomou, J.M. Leveque, Green Chemistry, 15 (2013) 2493-2501.
6. M. Regel-Rosocka, M. Wisniewski, Hydrometallurgy, 110 (2011) 85-90.
7. A. Cieszynska, M. Wisniewski, Sep.Purif. Technol., 80 (2011) 385-389.
106
FACILITATED TRANSPORT OF SELECTED ORGANIC ACIDS
THROUGH POLYMER INCLUSION MEMBRANES CONTAINING
1-ALKYL-1,2,4-TRIAZOLES AS CARRIERS
Piotr Gajewski, Marta Przewoźna, Mariusz B. Bogacki
Poznań University of Technology, Institute of Chemical Technology and
Engineering, Berdychowo 4, 60-965 Poznań, Poland
e-mail: piotrgajewskitch@wp.pl
Polymer inclusion membranes (PIM) are one of the types of membranes that
recently are more and more often tested from the point of view of releasing of
both organic and nonorganic compounds (1). Actually PIMs are used mainly in
transport of metal ions including zinc(II), copper(II), nickel(II), cobalt(II) and
many others. However, as it is presented in many publications, those
membranes could be used in transport of organic compounds (2) including
organic acids (3).
As it was shown in the previous studies conducted in our research group,
compounds from the group of azoles derivatives can play a role of the carriers
able to the transport of organic acids through the polymer inclusion
membranes (4,5).
In conducted studies, influence of alkyl chain length in 1-alky-1,2,4-triazoles
applied as a carriers and structure of organic acids on the transport rate of
chosen organic acids through the PIM were investigated. Obtained results have
shown that both alkyl chain length and structure of transported acid influence on
transport process. It was observed that the transport rate increases with
increasing alkyl chain length in applied carriers and achieves maximum value
for 9-11 carbon atoms in alkyl chain. For higher number of carbon atoms
transport rate decreases what could be connected with decreasing of
compatibility of these carriers with polymer matrix. Comparing influence of the
organic acids structure on transport process, it could be observed that transport
rate decreases with increase of molecular weight and acidic constant of
transported acids. At this stage it was not found out which effect has higher
influence on transport rate.
03/32/DSPB/0509 conducted at the Poznan University of Technology.
References
1. M.I.G.S. Almeida et al., J. Membr. Sci., 415-416 (2012) 9-23.
2. B.D. Smith et al., J. Inclus. Phenom. Mol., 32 (1998) 121-131.
3. M. Matsumoto et al., Separ. Sci. Technol., 47 (2012) 354-359.
4. M. Przewoźna et al., Separ. Sci. Technol., 49 (2014) 1745-1755.
5. P. Gajewski et al., Separ. Sci. Technol., 49 (2014) 1736-1744.
107
EXAMINATION OF THE FORMATION OF Cd(II) COMPLEXES
WITH 1-ALKYLIMIDAZOLE BY THE LIQUID-LIQUID PARTITION
METHOD
Elżbieta Radzymińska-Lenarcik
Department of Inorganic Chemistry, UTP University of Science and Technology,
Seminaryjna 3, 85-326 Bydgoszcz, Poland
e-mail: elaradz@utp.edu.pl
By using the liquid-liquid partition method, the formation of Cd(II) complexes
with 1-alkylimidazoles (L) (where alkyl = methyl, ethyl, propyl, butyl, pentyl,
hexyl, octyl, decyl, and dodecyl) has been studied at 25°C and at a fixed ionic
strength of the aqueous phase (I = 0.5; (HL)NO3, KNO3). The complexes were
extracted with 2-ethyl-1-hexanol and trichloromethane. The stability constants of
the (CdLn) complexes in aqueous solution as well as the partition ratios of the
extractable species were determined. The stability constants of the first (CdL),
second (CdL2) and third (CdL3) complexes did not depend on the alkyl chain
length in 1-alkylimidazole molecules, but for the fourth (CdL4) complexes they
increase with an increasing 1-alkyl chain length. It was shown that the partition
ratios increased with an increasing 1-alkyl chain length. The stability constants
were smaller than those previously studied for Co(II), Ni(II), and Cu(II)
complexes, but were higher than those for Zn(II). The stability constants and
partition ratios of the Cd(II) complexes for the second, third, and fourth step of
complexation (n = 2, 3 or 4) are higher because the octahedral and tetrahedral
complexes were formed in the aqueous solutions.
108
APPLICATION OF POLYMER MEMBRANES WITH 1-ALKYL-4METHYLIMIDAZOLE FOR RECOVERY OF ZINC FROM WASTE
Elżbieta Radzymińska-Lenarcik1, Małgorzata Ulewicz2
1 Department
of Inorganic Chemistry, University of Science and Technology,
Seminaryjna 3, 85-326 Bydgoszcz, Poland,
2 Department of General Building Engineering and Building Physics, Faculty of
Civil Engineering, Czestochowa University of Technology, 42-201
Czestochowa, Akademicka 3, Poland
e-mail: elaradz@utp.edu.pl
The disposal of post-production waste and spent solutions is an important
element of sustainable development, which enables considerable savings on
natural resources. Recovery of metals from aqueous solutions is important both
for economics and for the environment. In membrane techniques, which have
for some time become more and more widely used for removing non-ferrous
metal ions from aqueous solutions and post-production liquid waste in
laboratory conditions, the steps of extraction and re-extraction are carried out at
a time. The liquid membrane is a separate organic phase between two other
liquid, aqueous phases. The membrane processes are characterized by an
improved utilization of the ion carrier (extractant) being found within the organic
phase (membrane), in comparison with the conventional extraction system.
High selectivity coefficients for the separation process can be obtained using
suitably selected carriers having high affinities to one of the components of the
feed solution.
In this work, the authors present the results of their investigation into the
competitive transportation of Zn(II) from different equimolar mixtures of
transition metal ions such as Cu(II), Cd(II), Pb(II), Co(II), and Ni(II) ions across
polymer inclusion membranes containing 1-alkyl-4-methylimidazole (alkyl =
octyl, nonyl, decyl) from dilute model chloride and sulfate solutions as well as
from waste solutions. The findings of atomic force microscopy (AFM)
examinations as well as the thermograms of a polymer inclusion membrane
containing a derivative of imidazole were also presented. The PIM membrane
tested exhibit good stability, described using the Danesi’s thermodynamic
model. The stability of PIM with imidazole derivatives was confirmed in replicate
experiments. It was found that the transport of the investigated ions across
polymer membranes, depends on the membrane morphology (normalized flux),
and the carriers tested provide an efficient recovery of zinc from model solutions
as well as from actual waste solutions. More details will be presented in a
poster.
109
REMOVAL OF Zn(II), Cu(II), Co(II), Ni(II) FROM CHLORIDE
AND SULFATE SOLUTIONS WITH MIXTURES OF ACIDIC
AND BASIC EXTRACTANTS
Magdalena Regel-Rosocka, Marta Tarnowska, Agnieszka Markiewicz
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
Heavy metals play a crucial role in the chemical, paper, tannery industry (1).
These are the mining industry and production where processes with heavy
metals are applied being the source of wastewater containing salts of these
metals. The main source of acid solutions of heavy metals, such as Zn(II),
Cu(II), Co(II) and Ni(II), are chloride leaching or hot-dip galvanizing plants.
In the light of sustainable development it is important to recover all the valuable
and/or toxic substances, if the cost/benefit balance is maintained. Solvent
extraction can be an effective technique for purification of aqueous effluents
from metal ions. Since the beginning of the XXI-st century, ionic liquids
(imidazolium, ammonium, phosphonium) have been gaining importance in
separation processes (2).
The aim of the work is to investigate extraction-stripping of Zn(II), Co(II), Cu(II)
and Ni(II) from chloride solutions with binary mixtures of phosphonium ILs
(trihexyltetradecylphosphonium
chloride
Cyphos
IL
101,
trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl)phosphinate - Cyphos
IL 104), or methyltrioctylammonium chloride (Aliquat 336) with Cyanex 272
(bis(2,4,4-trimethylpentyl)phosphinic acid).
The following issues are investigated: i) the effect of initial pH of feeds on the
percentage extraction, ii) the composition and the molar ratio of organic
components of binary mixtures on metal ion extraction, iii) structure of
complexes formed by the metal ions with the extractants studied iv) the
presence of other ions in two- or four-ion mixtures on the selectivity of their
extraction.
Among these studied metal ions, Zn(II) is extracted the best both from two- and
four-ion mixtures with the binary mixtures of extractants used.
Acknowledgements: This work was supported by the 03/32/DS-PB/0501 grant.
References
1. M. Urbańska, G. Kłosowski, Ochr. Śr. Zasob. Natur., 51 (2012) 62-77.
2. M. Regel-Rosocka, K. Materna, "Ionic Liquids for Separation of Metal Ions and Organic
Compounds from Aqueous Solutions", Ionic Liquids in Separation Technology, Ed. by Pérez
De Los Ríos A., Hernández Fernández F. J., Elsevier, Netherlands-Oxford-Waltham 2014,
153-188, ISBN: 978-0-444-63257-9.
110
FIXED-BED ADSORPTION OF TRIAZINES
ON SPECIFIC POLYMERIC SORBENT
Sylwia Ronka1, Honorata Juskiewicz
1 Faculty
of Chemistry, Wroclaw University of Technology,
e-mail: sylwia.ronka@pwr.edu.pl
In order to obtain specific polymer adsorbent for triazine-based herbicides
removal, the poly(divinylbenzene) beads were synthesized in radical
polymerization using bead polymerization, and modified with maleic acid
anhydrate in Diels-Alder reaction (1). Resulted groups were subjected to
hydrolysis to get carboxyl groups. Carboxyl groups are able to form hydrogen
bonds, their position and distance between them allow for the formation of
complexes with adsorbate molecules such as triazines. Such specific,
directional interactions are responsible for better sorption and selectivity when
compared to the traditional polymeric adsorbents.
Sorption studies were carried out on a specific polymer sorbent for five
herbicides: simazine, atrazine, propazine, tertbuthylazine and metamitron.
Previous studies were able to determine the sorption maximum in the static
conditions for each tested herbicide (2). The current investigations were
performed in flow conditions separately for each triazine using 10 ppm
herbicide solutions. The contents of triazines were analyzed using UV/VIS
spectrophotometry technique. The results are shown in Figure 1.
Fig. 1. Breakthrough curves for adsorption of triazines, C0=10 ppm, flow rate=5 μL/s
Sorption capacity and sorption parameters for assessing the suitability of
obtained polymers in the industry were calculated. The efficiency of desorption
using ethyl alcohol was also examined.
Acknowledgements: The work was financed by a statutory activity subsidy from the Polish
Technology.
References
1. A. Mercier, H. Deleuze, O. Mondain-Monval, React. Funct. Polym., 46 (2000) 67-79.
2. S. Ronka, M. Kujawska, H. Juskiewicz, Pure Appl. Chem., 86(11) (2014) 1755-1769.
111
PREPARATION OF POLY (2-ACRYLAMIDO-2METHYLPROPANE SULFONIC ACID) (AMPS) GRAFTED ONTO
CROSSLINKED POLY(VINYLBENZYL CHLORIDE) RESIN FOR
REMOVAL OF ATRAZINE FROM WATER
Fatih Bildik1, Bahire Filiz Senkal1, Tuba Şişmanoğlu2, Erdem Yavuz1
1 Istanbul
Technical University, Department of Chemistry, Maslak 34469
Istanbul/TURKEY,
2 Istanbul University, Engineering Faculty, Department of Chemistry, Avcılar,
Istanbul/TURKEY
e-mail: bsenkal@itu.edu.tr
Among the numerous agrochemicals in common use, atrazine is one of the
most widely applied herbicides in many countries. It has been detected at high
concentrations in ground- and surface waters all over Europe and North
America because of extensive usage, ability to persist in soils, low sediment
partitioning, slow rate of degradation and its tendency to migration with water
(1). Therefore, atrazine removal from water is widely studied using various
materials. One of the most efficient methods of water purification is adsorption
using polymeric materials, which can be easily modified and regenerated.
In this study, poly(AMPS) was grafted onto crosslinked poly(vinylbenzyl
chloride) (PVBC) beads through the chloromethyl group present in the resin
using ATRP polymerization method (Scheme 1).
PP
CH2 Cl
CuCl,CuCl2, ligand
P
CH2
CH2-CH
n
C=O
AMPS
NH
H3C
C
CH3
CH2
SO3H
Scheme 1. Preparation of core-shell type crosslinked polymeric resin
The resulting core-shell type polymeric sorbent has been demonstrated to be an
efficient sorbent for removal of atrazine. Effects of initial atrazine concentration,
pH and temperature on the sorbent with the batch method were investigated.
Reference
1. N. Graziano et al., Environ. Sci. Technol., 40 (2006) 1163-1171.
TRANSIENT PROCESSES IN MODEL CASCADES
112
A. Yu. Smirnov1, G. A. Sulaberidze1, V. D. Borisevich1, S. Zeng2, D. Jiang2
1 National
Research Nuclear University MEPhI, Moscow, Russia,
2 Tsinghua University, Beijing, P.R. China
e-mail: a.y.smirnoff@rambler.ru
The increased use of stable isotopes for various applications in basic research,
medicine and life sciences, nuclear power, etc. demands a new level of solving
the problem of optimization for the multi-isotope mixtures in separation
cascades. At the moment the various mathematical models of molecular
selective mass transfer in cascades and corresponding methods of numerical
simulation of their characteristics depending on the efficiency criterion under
consideration, are discussed. Being very useful and convenient tool for design
and optimization of multistage separation installations, the model cascades play
the important role in the theory of isotope separation in cascades (1,2).
In the theory of the separation of multicomponent mixtures is widely used socalled Q-cascade (3,4). However, so far only the stationary mass transfer has
been a subject of the research in a Q-cascade. At the same time in practical
terms the interest is to study the peculiarities of the non-stationary mass
transfer in Q-cascades for separation of multicomponent isotope mixtures and
to assess its time-to-steady state. Today, a similar problem has been solved
only for the case of the symmetric countercurrent cascade, which demanded
relatively complex procedures of numerical calculation of the cascade
parameters in the transient mode of its operation.
The model of transient multicomponent mass transfer in a Q-cascade
connected to the infinite reservoir is developed in this study. With its help it was
identify the following important peculiar properties:
• in a transient mode of operation of a Q-cascade the component concentrations
of a separated mixture may have maximums and minimums in the product flow
of a cascade;
• the regularities of the transient processes in a Q-stage have the qualitative
agreement with that of the numerical simulation of non-steady mass transfer of
the multicomponent isotope mixtures in other cascades. This fact confirms the
possibility to use a Q-cascade for analysis of the regularities of non-stationary
mass transfer in cascades and analytical assessment of its key parameters.
References
1. G.A. Sulaberidze et al., Sep. Sci. Technol., 36(8/9) (2001) 1769-1817.
2. T. Song et al., Sep. Sci. Technol., 45 (2010) 2113-2118.
3. V.D. Borisevich et al., Chem. Eng. Sci., 66 (2011) 393-396.
4. S. Zeng et al., Sep. Sci. Technol., 47/11 (2012) 1591-1595.
113
PUROLITE S 940 AND PURLITE S 950 IN HEAVY METAL IONS
REMOVAL FROM ACIDIC STREAMS
Weronika Sofińska-Chmiel1, Dorota Kołodyńska2
1 Analytical
Laboratory, Faculty of Chemistry, Maria Curie Skłodowska
University, 20-031 Lublin, Poland,
2 Department of Inorganic Chemistry, Faculty of Chemistry, Maria Curie
Skłodowska University, Lublin, 20-031, Poland
e-mail: wschmiel@umcs.pl
As a result of conducting various electroplating processes, the environment gets
infected by a whole range of toxic chemicals. From an ecological point of view,
removal of heavy metal ions that adversely affect the environment is of
significant importance. The metals used in surface treatment have a particularly
negative impact on the environment and human health are cadmium, chromium,
nickel, lead, copper, cobalt, iron and zinc. Therefore efficient and economical
processes for removal of heavy metal ions from industrial wastewater are
searched for. For the treatment of industrial wastewaters chelating ion
exchangers can be applied.
According to the literature, chelating ion exchangers containing
aminophosphonic functional groups exhibit high productivity in removal of
Fe(III), Co(II) and Ni(II) from acidic solutions (1). They also have a poor affinity
for Ca(II) and Mg(II) ions. The examples of such ion exchangers are Purolite S
940 and Purolite S 950. For the practical use of the above mentioned ion
exchangers in the process of wastewater treatment, their physicochemical and
kinetic studies were carried out. Sorption capacities of those ion exchangers
were determined depending on the contact time and the concentration in the
initial phase. The determined parameters were aimed at optimizing Fe(III),
Co(II) and Ni(II) sorption particularly the influence of chloride ions. Moreover,
spectroscopic and microscopic studies of Purolite S 940 and Purolite S 950 ion
exchange resins before and after sorption process were also carried out. The
study allowed to determine correlation between the chemical structure of the ion
exchange resins under investigations and the efficiency of Fe(III), Co(II) and
Ni(II) sorption.
References
1. R. Janceviciute, A. Gefeniene, J. Environ. Eng. Landsc., 14 (2006) 191-197.
114
REMOVAL OF Cu(II) USING ION EXCHANGE RESINS WITH
ANIONOPHOSHONIC FUNCTIONAL GROUPS
Weronika Sofińska-Chmiel1, Dorota Kołodyńska2, Ewaryst Mendyk1 and
Zbigniew Hubicki2
1 Analytical
Laboratory, Faculty of Chemistry, Maria Curie Skłodowska
University, 20-031 Lublin, Poland,
2 Department 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 physicochemical
properties of chelating ion exchangers with aminophosphonic functional groups
before and after Cu(II) sorption. The study was carried out on the Purolite S 940
and Purolite S 950. They are macroporous aminophosphonate chelating resins,
designed for removal of cations of such toxic metals as Pb(II), Cu(II) and Zn(II)
from industrial effluents at low pH. Their use can be recommended where it is
necessary to remove Ca(II) or Mg(II) in order to avoid possible precipitation (1).
For the practical use of the studied ion exchangers in wastewater purification,
sorption capacity of the above mentioned ions was determined depending on
the contact time and the initial concentration. The kinetic parameters were
determined in order to optimize Cu(II) ions sorption concerning influence of
chloride and sulphate ions.
There are many research techniques used for measuring physicochemical
properties of sorption materials. The most preferred technique is photoelectron
spectroscopy (1,2). In order to investigate the properties of Purolite S 940 and
Purolite S 950 before and after the sorption process Prevac Ultra High Vacuum
multi-chamber analytical system was applied.
Table 1. The elemental composition of Purolite S 940 and Purolite S 950 determined by
the XPS method
Sample
Purolite
S-940
C 1s
284.7
% Mass
concn.
57
Na 1s
1071.7
9.5
13.7
Name
Position
%Atom
concn.
42.8
P 2p
132,2
7.6
14.6
Cl 2p
198.2
2.9
6.4
N 1s
398.7
3.3
2.9
O 1s
531.1
19.7
19.7
Sample
Purolite
S-950
C 1s
284.7
% Mass
concn.
56.8
Na 1s
1071.2
8.6
N 1s
398.7
4.4
5.0
P 2p
132.7
9.7
24.2
O 1s
530.6
20.5
26.4
Name
Position
%Atom
concn.
54.9
15.9
References
1. http://www.purolite.com/relid/619158/isvars/default/chelation_resins.htm
2. M.C. Biesinger et al., App. Surface Sci., 257 (2011) 2717-2730.
115
APPLICATION OF PSEUDO-EMULSION BASED HOLLOW FIBER
STRIP DISPERSION (PEHFSD) FOR RECOVERY OF Zn(II)
Katarzyna Staszak1, Karolina Wieszczyka1, Magdalena Regel-Rosocka1,
Aleksandra Wojciechowska1, M. Teresa A. Reis2, M. Rosinda C. Ismael2, M.
Lurdes F. Gameiro2, Jorge M.R. Carvalho2
(12 pt)
1 Poznań University of Technology, Institute of Chemical Technology and
Engineering, ul. Berdychowo 4, 60-965 Poznań, Poland,
2 CERENA – Centre for Natural Resources and the Environment, Department of
Chemical Engineering, Instituto Superior Técnico, Universidade de Lisboa, Av.
Rovisco Pais, 1049-001 Lisboa, Portugal
e-mail: Katarzyna.Staszak@put.poznan.pl
(12 pt,)
Various techniques of regeneration of spent pickling solutions, including the
methods with acid recovery, such as diffusion dialysis, electrodialysis,
evaporation, precipitation and spray roasting as well as those with acid and
metal recovery: ion exchange, retardation, adsorption, crystallization and
membrane extraction are proposed in literature (1). Currently, there is a
tendency to combine various techniques into hybrids, e.g. separation fully
integrating extraction and stripping in a membrane contactor. The new
technique known as pseudo-emulsion based hollow fiber strip dispersion
(PEHFSD) was proposed in the literature (2) for the recovery of metal ions.
The aim of this work is the removal and recovery of Zn(II) ions by pseudoemulsion based hollow fiber strip dispersion (PEHFSD) with newly synthesized
pyridinium ketoxime salts as extractants. The approach of the present work
includes the study of various experimental parameters like metal, salt and acid
concentrations in the feed solution. The experimental setup used for carrying
out PEHFSD experiments is shown in Figure 1. In this schematic diagram HF
represents the microporous fiber module, which was a Liqui-Cel® Extra-Flow
2.5 in. × 8 in. membrane contactor from Celgard (USA).
Fig. 1. PEHFSD experimental setup
Acknowledgements: This research was supported with 03/32/DS-PB/0501 and 03/32/DSPB/0500 grants and project UID/ECI/04028/2013 (FCT, Portugal). PEHFSD studies were
realized in the frame of Polish-Portuguese scientific and technological cooperation „Selective
extractants for the removal of minor metallic elements from chloride spent pickling baths”.
References
1. M. Regel-Rosocka, J. Hazard. Mater., 177 (2010) 57-69.
2. A.K. Pabby, S.S.H. Rizvi, A.M. Sastre, Handbook of Membrane Separations: Chemical,
Pharmaceutical, Food, and Biotechnological Applications, CRC Press, Boca Raton, FL, USA
2008.
116
ON THE SEPARATIVE POTENTIAL (VALUE FUNCTION) FOR
SEPARATION OF MULTICOMPONENT MIXTURES: STATUS OF
THE PROBLEM
V. D. Borisevich, A. Yu. Smirnov, G. A. Sulaberidze
National Research Nuclear University MEPhI
31 Kashirskoe Shosse, Moscow 115409, Russian Federation
e-mail: sula39@mail.ru
There is no complete clarity in a number of issues in the theory of
multicomponent mixtures separation in cascades that are of great practical
importance. Among them is the definition of the separative potential, in other
words the value function and associated with it the efficiency criteria for a single
separation element and cascade. This circumstance is due to the impossibility
to build in practice the separation cascade, in which could be implemented the
condition of no-mixing concentrations at the points of flow confluence at the
entrance of its stages. In numerous published papers on the matter, their
authors often use different axiomatic approaches based on various
assumptions. As a result, they obtain noticeably differ from each other
separative potentials (1-2).
In the present research it is examined various separative potentials introduced
in manifold papers and carry out comparison of the results of separation
cascade optimization performed with their use as well as with application as the
efficiency criterion the total flow in a cascade. It demonstrates that the choice of
the separative potential depends on the characteristics of the separated isotope
mixture and the peculiarities of the applied separation process. These features
do not allow to establish a priori which of the known separative potentials is the
best one to solve a specific separation problem. The separative potential that
allows estimating the minimum separation work that must be expended for
production of a unit mass of a target component with its given concentration is
discussed in the paper. The concept of the proposed efficiency criterion is
based on the theory of a Matched Abundance Ratio Cascade (MARC)
developed by De la Garza (3). Later this concept has been further developed in
(4-9).
References
1. V.A. Palkin, At. Energy, 95(5) (2003) 786-793.
2. T.M. Song et al, Proc. 9th Intl. Workshop on Separation Phenomena in Liquids and Gases,
2006, Beijing, China, 132.
3. A. De la Garza, Chem. Eng. Sci., 18 (1963) 73-82.
4. E. Von Halle, Proc. 1st Workshop on Separation Phenomena in Liquids and Gases,
Darmstadt, 1987, 325.
5. H.G. Wood et al., Sep. Sci. Techol., 34(3) (1999) 343-357.
6. G.A. Sulaberidze et al., Sep. Sci. Techol., 36(8/9) (2001) 1769-1817.
7. V.D. Borisevich et al., Ars Separatoria Acta, 2 (2003) 107-124.
8. G.A. Sulaberidze et al., Theor. Found. Chem. Eng., 42(4) (2008) 347-353.
9. T. Song, Sep. Sci. Technol., 45 (2010) 2113-2118.
117
THE RESPONSE SURFACE ANALYSIS FOR ESTIMATION
OF THE MASS TRANSFER COEFFICIENT IN PERTRACTION
Piotr Szczepański, Grażyna Szczepańska
Nicolaus Copernicus University in Toruń, Faculty of Chemistry,
ul. Gagarina 7, 87-100 Toruń, Poland
e-mail: piotrs@chem.umk.pl
The results of previous studies demonstrated that some molecular descriptors
(MD) derived from the structure of organic solvent are good variables enabling a
quantitative correlation of the benzoic acid fluxes with the physicochemical
properties of an organic solvent (described by MD) used as a liquid membrane
(1).
In this presentation a new method for estimation of the overall mass transfer
coefficient from empirical models is presented. For this purpose the response
surface methodology (2) was applied and the simultaneous effect of operating
parameters such as: feed phase concentration (cf), liquid membrane volume
(VLM), and molecular descriptor (MD, representing the properties of organic
solvent) on the maximum stripping fluxes (Jmax) of benzoic acid in an agitated
bulk liquid membrane system was investigated.
The results indicated that, the response surface methodology (empirical
modeling) enables the determination of the parameter (apparent mass transfer
coefficient, kapp, [cm/s]), which can be considered as the estimation of the
overall mass transfer coefficient (physicochemical parameter). For example, the
apparent permeability coefficient relationship vs. liquid membrane volume (V LM)
and reciprocal hyper-detour index (Rww) is presented by the following equation:
kapp= 2.09810-4 – 6.25110-7VLM – 5.36210-6 Rww + 1.77610-8VLM Rww (1)
For the liquid membrane made of octane (Rww=10.564) of 50 cm3 volume, the
apparent mass transfer coefficient calculated from Eq. (1) amounts 1.31310-4
cm/s and is equal to the experimentally evaluated (kapp = 1.31310-4 cm/s) one.
It should be stated here that these equation one could obtained because near
linear relationship between Jmax and cf in the studied system was observed. It
was also found that, the linear empirical model with two- and three interaction terms (3)
between the operational parameters describes over 99 % of the total variance of the
benzoic acid fluxes vs. selected variables.
The external and cross validation methods were successfully applied in order to
evaluate the predictive accuracy of the constructed models and confirms that
the squared Moriguchi octanol-water partition coefficient (MLOGP2) and
reciprocal hyper-detour index (Rww) are the best molecular descriptors in the
models with three factor interaction terms.
References
1. P. Szczepański, Sep. Purif. Technol., 71 (2010) 121-127.
2. L.S. Aiken, S.G. West, Multiple Regression: Testing and Interpreting Interactions, Sage
Publications, Inc., Newbury Park, 1991.
3. R.H. Myers, D.C. Montgomery, C.M. Anderson-Cook, Response surface methodology.
Process and product optimization using designed experiments, John Wiley & Sons, Inc.,
Hoboken, New Jersey, 2009.
118
TRANSPORT AND SEPARATION OF PHENOL
AND p-NITROPHENOL IN AN AGITATED BULK LIQUID
MEMBRANE SYSTEM. EXPERIMENTAL AND THEORETICAL
STUDY BY NETWORK ANALYSIS
Piotr Szczepański, Romuald Wódzki
Nicolaus Copernicus University, Faculty of Chemistry,
ul. Gagarina 7, 87-100 Toruń, Poland
e-mail: piotrs@chem.umk.pl
A predictive mathematical model based on pseudo-thermodynamic network
analysis was applied to simulate the pertraction and separation of phenol and pnitrophenol in the agitated bulk liquid membrane system (ABLM). The transport
of phenol and p-nitrophenol in this system involves three steps, i.e. extraction,
diffusion, and re-extraction with the neutralization reaction in the stripping
solution (NaOH).
A bond-graph method in the version proposed by Schnakenberg (1) was
applied in order to obtain the corresponding mathematical model (a set of
ordinary differential equations). These equations were numerically solved using
Berkeley Madonna 8.3 software (fourth order Runge-Kutta method) to predict
the time evolution of local fluxes and concentrations of phenol and p-nitrophenol
in the ABLM system. The appropriate calculations were carried out with data
accessible in literature (diffusion coefficients, thickness of diffusion layers) or
measured in independent experiments (extraction and re-extraction kinetic
constants, equilibrium distribution coefficient).
Some typical results of numerical calculations were compared with experimental
data. An example of the phenol and p-nitrophenol concentration prediction in
the feed, membrane, and stripping solution, as well as separation coefficient as
a function of time, are presented below.
It can be concluded that the presented model predicts accurately the timedependent concentration profiles and separation in the ABLM system. The
equations used in the model (to describe local fluxes and time evolution of local
concentrations) are generic equations, valid for any ABLM pertraction system,
i.e. they are applicable after a respective modification to describe weak bases
and carboxylic acids transport, too.
References
1. J. Schnakenberg, Thermodynamic Network Analysis of Biological Systems, Springer Verlag,
Berlin, 1977, 4-65.
119
MODIFICATION OF POLY(GLYCIDYL METHACRYLATE)
GRAFTED ONTO CROSSLINKED POLY(3-CHLORO-2HYDROXYPROPYL METHACRYLATE-METHYL
METHACRYLATE (MMA)-ETHYLENE GLYCOLE
DIMETHACRYLATE (EGDMA)) WITH AMINO-BIS-(CIS-PROPAN
2,3 DIOL) FUNCTIONS FOR REMOVAL OF BORON FROM
WATER
Gulcin Torunoglu Turan, B. Filiz Senkal
Istanbul Technical University. Department of Chemistry. Maslak 34469 Istanbul/
Turkey
e-mail: torunoglug@itu.edu.tr
Polymer supported core-shell type functions amino-bis-(cis-propan-2,3-diol)
have been shown to be efficient in chelation with boric acid and can be used for
removal of boric acid at ppm levels. Crosslinked poly(3-chloro-2-hydroxypropyl
methacrylate-methyl methacrylate (MMA)-ethyleneglycole dimethacrylate
(EGDMA)) terpolymer was prepared by suspension polymerization. Graft
copolymerization of glycidyl methacrylate (GMA) onto the resin was carried out
using ATRP method. The epoxy rings in grafted PGMA resin reacted with
excess of diallylamine to obtain diallyl functions. Then, the diallyl modified resin
was interacted with hydrogen peroxide, in presence of OsO 4 catalyst yields
polymer supported amino-bis(cis-propane 2,3-diol) functions (Scheme 1).
CH 3
P
OH
CH 3
P
+
CH 2-C
CH 2-C
HN
n
n
OH
C= O
C= O
O
O
CH 2-CH-C H2
CH 2-CH-CH2 N
OH
O
H2O2 OsO4 (cat.)
CH 3
P
CH 2-C
OH
n
OH
C= O
O
CH 2-CH-C H2 N
OH
OH
OH
OH
Scheme 1. Preparation of core-shell type crosslinked polymeric resin with amino-bis
(propane cis 2,3 diol) groups
The resulting polymeric sorbent has been demonstrated to be an efficient and
regenerable specific sorbent for removal of boron. Kinetics of boron sorption
and regeneration of the polymer was investigated.
120
SOLVENT EXTRACTION OF PRECIOUS METAL IONS WITH
TRIMETHYLACETAMIDE TYPE OF TRIDENT MOLECULE
Yuki Ueda, Shintaro Morisada, Hidetaka Kawakita, Keisuke Ohto
Department of Chemistry and Applied Chemistry, Faculty of Science and
Engineering, Saga University, Honjo-1 Saga, Japan
e-mail: 14634001@edu.cc.saga-u.ac.jp
Trident molecules based on alkyl trimethylol have been prepared as a metal
extraction reagent. The trident molecule has three hydroxyl groups for chemical
modification, strong binding property as a tridentate C3 symmetry, size
recognition due to having relatively rigid coordination site. In the present study,
selective extraction of precious metals with phenylurea type of trident molecule
has been investigated.
%Extraction
The extraction reagent shown in Figure 1 was synthesized from 1,1,1tris(aminomethyl)-9-decene based on 10-undecenal via four steps. The product
was identified by 1H-NMR and FT-IR spectra. Extraction experiment was carried
out by conventional batch method. The organic phase was prepared by
dissolving the extraction reagent in
chloroform to be 5 mM (M = mol dm-3).
The aqueous phase was prepared by
dissolving metal salt in concentrated
HCl solution. Equal volumes of both
CH2=CH(CH2)7C
phases were shaken at 303 K for 20 h.
After
shaking,
the
metal
concentrations were measured by
ICP-AES (Shimadzu ICPS-8100).
Figure 2 shows effects of HCl
Fig. 1. Chemical structure of 1,1,1concentration on the extraction tris(trimethylacetamidomethyl)-9-decene
percentage of precious metal ions with
the trimethylacetamide type of trident
100
molecule. The extraction percentage
3+
Au
2+
3+
2+
4+
Pd4+
of the Au , Pd , and Pt
were
Pt 3+
80
decreased with increasing the HCl
Rh
3+
3+
Ir 3+
concentration. Rh
and Ir
were
60
hardly extracted at any concentration
of HCl. Based on these results,
40
extraction mechanism of Au3+, Pd2+,
and Pt4+ with the trimethylacetamide
20
type of trident molecule were
determined by slope analysis and
0
peak shift for the 1H-NMR and FT-IR
0.01
0.1
1
10
spectra of extraction reagent.
[HCl] / M
Acknowledgements: This research was partly
financed Research Fellowships of Japan
Society for the Promotion of Science for
Young Scientists.
Fig. 2. Effect of HCl concentrations on
extraction percentage of PGMs with the
trimethylacetamide type of trident
molecule
121
OXIDATIVE ADSORPTION OF ARSENIC WITH
N-METHYL GLUCAMINE BASED ADSORBENT
AND MANGANESE DIOXIDE
Toshiyuki Umebayashi, Syouhei Nishihama, Kazuharu Yoshizuka
Hibikino 1-1, Kitakyusyu 808-0135, Japan
e-mail: v4maa003@eng.kitakyu-u.ac.jp
1. Introduction
Arsenic (As) has high toxicity and WHO guideline value for drinking water is
limited to 0.01 mg/L. Removal of As from water environment is therefore
required, because As is frequently included in groundwater and hot spring
water. In the present work, adsorptive removal of arsenic was investigated with
Chelest fiber having N-methylglucamine group, followed by oxidation of As(III)
to As(V) with γ-MnO2.
Figure 1 shows the effect of pH on the
adsorption of As(III) or As(V) with Chelest fiber.
In acidic pH region, high adsorption ability for
As(V) was obtained, while adsorption of As(III)
was low. Chelest fiber possesses high affinity
for oxyanion of As(V), H2AsO4-.
Oxidative adsorption of As(III) was then
investigated by employing Chelest fiber as
adsorbent and γ-MnO2 as oxidizing reagent
(Figure 2). Adsorption behaviour of As with the
mixture was similar to that of As(V) with Chelest
fiber, indicating that the oxidation of As(III) was
successfully progressed with the γ-MnO2. In
addition, adsorption percentage of As was
increased by increasing amount of γ-MnO2.
Optimization of the oxidative adsorption process
is expected to promote effective removal of As
from water environment.
122
1.5
● As(III)
○ As(V)
qAs [mmol g-1]
1
0.5
0
2
3
4
5
6
pH eq.
7
8
9
Fig. 1. Effect of pH on
adsorption of As(III) and
As(V) with Chelest fiber
100
80
Adsorption [%]
2. Experimental
Adsorption of As(III) and As(V) was carried out
by shaking 10 mL of aqueous solution ([As(III)]
= [As(V)] = 10 mmol/L) and 0.02 g of Chelest
fiber (GRY-HW, Chelest Co.). Oxidative
adsorption of As(III) was carried out by shaking
20 mL of aqueous solution ([As(III)] = 2.74
mmol/L), 0.1 g of Chelest fiber, and 0.01 g or
0.03 g of γ-MnO2 (Wako Pure Chemical
Industries, Ltd.). Concentrations of As were
determined by ICP-AES.
60
40
20
0
Additional amount of γ-MnO2
● 0.01 g ○ 0.03 g
2
3
4
5
6
pH eq.
7
8
Fig. 2. Oxidative adsorption
of As(III) with mixture of
Chelest fiber and γ-MnO2
9
STRONTIUM ADSORPTION ON IONIC LIQUID IMPREGNATED
FLORISIL. FIXED-BED COLUMN STUDIES
Lavinia Lupa1, Adriana Popa2, Raluca Voda1, Petru Negrea1, Mihaela
Ciopec1, Adina Negrea1
1 University
Politehnica Timisoara, Faculty of Industrial Chemistry and
Environmental Engineering, 6 V. Parvan Blv, RO-300223, Timisoara, Romania,
2 Institute of Chemistry Timisoara of Romanian Academy, Romanian Academy,
24 Mihai Viteazul Blv., RO-300223 – Timisoara, Romania
e-mail: raluca.voda@upt.ro
In the present work the adsorption of strontium ions from aqueous solutions on
ionic liquid impregnated Florisil was studied using a fixed-bed column. As a
ionic liquid trihexyltetradecylphosphonium chloride – (Cyphos IL-101) was
chosen due to its performance in the removal process of radionuclides using
liquid-liquid extraction.
The impregnation of the ionic liquid onto the solid support was realized through
ultrasonication and than the sample was dried using the rotavapor system. The
obtained impregnated materials have been subjected to FTIR - Fourier
transform infrared spectroscopy, scanning electron microscopy (SEM), and
energy dispersive X-Ray analysis (EDX).
The adsorption process was studied using different bed heights (3 and 5 cm) of
IL impregnated Florisil, different column diameter (1 and 2 cm), various
strontium ions concentrations (10, 20 and 30 mg/L) and various flow rate (3, 5
and 7 mL/min). The experimental data were correlated using the bed depth
service time (BDST) model. The increase in flow rate decreases the
breakthrough time, exhaustion time and uptake capacity of the strontium ions
due to insufficient residence time of the strontium ions in the column. The
column was regenerated with 5% HCl solution, and the adsorbent was used in 4
adsorption-desorption cycles. It was observed that after the first desorption
cycle the adsorption efficiency decreases with 20%, then it remains constant for
the last cycles.
The influence of other cations (Ca2+ and K+) on the strontium adsorption
efficiency was also studied using various concentrations (CMn+ < CSr2+; CMn+ =
CSr2+; CMn+ > CSr2+). It was observed that if the concentrations of the other cation
are smaller or equal with the initial concentration of strontium ions the
adsorption efficiency is not strongly influenced, but higher concentrations lead
to the decrease of the strontium ions removal efficiency.
The present study showed that the strontium ions can be efficiently removed
from aqueous solutions through adsorption onto Florisil impregnated with
Cyphos IL-101.
Acknowledgments: „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”.
123
THE DEVELOPMENT OF A NEW EFFICIENT ADSORBENT FOR
THE REMOVAL OF METHYLENE BLUE
Raluca Vodă, Lavinia Lupa, Adina Negrea, Mihaela Ciopec, Petru Negrea,
Corneliu M. Davidescu
University Politehnica Timisoara, Faculty for Industrial Chemistry and
Environmental Engineering, Bv. Parvan no. 6, Timisoara, RO-300223, Romania
e-mail: raluca.voda@upt.ro
The authors present the experimental results of the structural investigations and
thermal analysis of cadmium ferrioxalate coordination compound, precursor of
the cadmium ferrite. The compound was obtained by a new unconventional
method, through the reaction of 1,2-ethanediol with Fe(NO3)3·9H2O and
Cd(NO3)2·4H2O in the presence of nitric acid.
The synthesized precursor was characterized by chemical analysis, IR
vibrational spectrum and thermal analysis. The oxide obtained through
thermolysis was characterized by IR spectroscopy, XRD (X-ray diffraction) and
SEM (scanning electron microscopy).
The obtained cadmium ferrite was used as adsorbent material in the removal
process of Methylene Blue (MB) from aqueous solutions. The studied material
presented good performance in the removal process of MB from aqueous
solutions. The studied cadmium ferrite developed an efficiency over 99% and
an adsorption capacity of 4.67 mg MB/g of adsorbent when is used a S:L ratio
of 0.02 g:10 mL aqueous solution for 1 h of shaking. It was found that the
adsorption of MB onto studied material is described by the pseudo-secondorder kinetic model. The equilibrium sorption data were modelled using
Freundlich and Langmuir isotherms.
Acknowledgments: This work was partially supported by the strategic grant
POSDRU/159/1.5/S/137070 (2014) of the Ministry of National Education, Romania, co-financed
by the European Social Fund – Investing in People, within the Sectoral Operational Programme
Human Resources Development 2007-2013.
124
APPLICATION OF β-DIKETONES DERIVATIVES FOR
SELECTIVE SEPARATION OF COPPER IONS IN THE
TRANSPORT PROCESS ACROSS A POLYMERIC INCLUSION
MEMBRANE
Katarzyna Witt, Elżbieta Radzymińska-Lenarcik, Włodzimierz Urbaniak
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
Non-ferrous metals recovering from the ores and metal-bearing wastes such as
flue dusts, melting losses, slimes and spent technological liquors is based either
on pyrogenic or hydrometallurgical (wet) technologies. Selection of the
appropriate manufacturing process depends on their useful metal content. In a
typical wet process, among the four basic technologies, i.e. leaching, phase
separation, extraction of metal ions from aqueous solutions and deposition of
the ions from the aqueous phase, of particular interest is separation of the ions
in aqueous solution which has direct bearing on the purity of a final product.
Poly(vinyl chloride) membranes doped with β-diketones derivatives as carriers
were applied for the investigation of the selective transport of Cu(II) ions from
an aqueous nitrate source phase. The influence of the substituent of β-diketone
molecules on the selective recovery of copper was also presented.
The polymer membranes were characterized by the SEM (Scanning Electron
Microscope analysis) and TG (Thermogravimetric analysis).
More details will be presented on poster.
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. UDAPOIG.01.03.02-04-077/12-00, financed by the European Regional Development Fund (ERDF)
(85% of co-financing) and from a designated subsidy (15% of co-financing).
125
INVESTIGATION OF CHROMIUM (III AND VI) IONS SORPTION
ON WEAKLY BASIC ANION EXCHANGER
Grzegorz Wójcik, Zbigniew Hubicki
University of Maria Curie-Skłodowska, Faculty of Chemistry, Department of
Inorganic Chemistry Pl. M. Curie-Sklodowskiej 2, 20-031 Lublin, Poland
e-mail: grzegorzwojcikumcs@wp.pl
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. 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. 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 lots of 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. 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 Purolite A 830 was used for removal of chromium(VI and III) ions.
Purolite A 830 is a macroporous weakly basic anion exchanger. 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 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 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.
126
NEW SOLVENT IMPREGNATED RESIN AMBERLITE XAD 7 HP
FOR RECOVERY OF GOLD(III) IONS FROM METALLIC
SECONDARY SOURCES
Grzegorz Wójcik, Zbigniew Hubicki, Magdalena Górska
University of Maria Curie-Skłodowska, Faculty of Chemistry, Department of
Inorganic Chemistry Pl. M. Curie-Sklodowskiej 2, 20-031 Lublin, Poland
e-mail: grzegorzwojcikumcs@wp.pl
Waste electrical and electronic equipment (WEEE) is considered to be one of
the fastest growing waste streams in Europe (1). Growing demand for gold
makes it crucial to recover gold from the inevitably increasing waste products
(2). The process of recovery makes sense only if the cost of recovery is much
lower than the value of the precious metal. Besides, restrictions imposed on
waste disposal and stringent environmental regulations demand eco-friendly
technologies (3).
The solvent impregnated resin (SIRs) consists of commercially available
macroporous resins impregnated by an extractant (4). The immobilization of the
extractant in SIRs, avoids emulsification and simplifies the phase separation
after extraction and due to the impregnation, the loss of extractant into the
aqueous phase during extraction decreases (5).
There were carried out laboratory studies of selective removal of gold(III) from
real solution on the solvent impregnated non-ionic aliphatic acrylic polymer,
Amberlite XAD 7HP using Cyanex 301.
The solution was prepared by leaching of pins in the hydrochloric acid-hydrogen
peroxide system. The pins were recycled from the 8P8C modular plug used
commonly to connect personal computers onto local-area networks (LAN),
especially Ethernets.
Gold concentration was determined by the AAS method. The gold(III) ions
concentration was 16.53 ppm. The real solution contained also Cu2+, Co2+, Fe3+,
Ni2+ and Zn2+ ions. In these experiments % R of gold(III) was obtained. The
results demonstrated that % R was better for Amberlite XAD 7HP impregnated
with Cyanex 301 (97,88 %) than that of Amberlite XAD 7HP before
impregnation (62,73 %). Batch desorption experiments were carried out using
5% thiourea in the 0.1 M HCl solutions.
The described method using Amberlite XAD 7HP impregnated with Cyanex 301
for selective separation of ions gold(III) proved to be effective for recovery of
gold from secondary metallic sources.
References
1. M. Bigum et al., J. Hazard. Mater., 207-208 (2012) 8-14.
2. S. Syed, Hydrometallurgy, 115-116 (2012) 30-51.
3. S. Syed, Hydrometallurgy, 82 (2006) 48-53.
4. B. Burghoff et al., React. Funct. Polym., 68 (2008) 1314-1324.
5. B. Burghoff et al., React. Funct. Polym., 70 (2010) 41-47.
127
THERMORESPONSIVE MOLECULARLY IMPRINTED POLYMER
FOR FAST SORPTION AND DESORPTION OF DIETHYL
PHTHALATE
Wrocław University of Technology, Faculty of Chemistry, 50-370 Wrocław,
Wybrzeże Wyspiańskiego 27, Poland
e-mail: joanna.wolska@pwr.edu.pl
Molecularly imprinted polymers (MIPs) have been proved to be material with a
highly specific molecular recognition ability. With tailored selectivity, easy
preparation, and chemical robustness, MIPs can be used as a specific affinity
matrix for a target template (1).
Stimuli responsive polymers are a class of materials that are able to respond to
external stimuli (e.g. temperature, pH, or ionic strengh) and change their
properties accordingly. By integrating the smart material technology, “smart”
MIPs with self-controlling abilities have been successfully designed and
prepared to produce environmentally responsive synthetic structures capable of
specific, high-affinity binding (1,2). Among them, thermoresponsive MIPs, which
respond to temperature changes, are the most extensively studied polymers.
A thermoresponsive molecularly imprinted polymer (TS-MIP) has been
specifically synthesized as a “smart” material for the removing of one of the
endocrine disruptors - diethylene phthalate (DEP). The “smart” block polymers
were synthesized from N-isopropylacrylamide (NIPAM), methyl methacrylate
(MMA) and ethylene glycol dimethacrylate (EGDMA). The studies have focused
on selection of monomers composition, kind of solvent and amount of template
to obtain the best material. The molecular recognition ability towards DEP has
been studied. The synthesized materials displayed significant dependence on
temperature compared with their non-imprinted anologues. The greatest affinity
was achievied at about 30°C. The highest affinity towards template had material
prepared from NIPAM:MMA 3:7 ratio, with the 60% of crosslinker and toluene
as solvent. The best conditions for desorption of DEP was to keep MIP in water
at 60°C. It allowed to remove more than 80% of adsorbed diethylene phthalate.
Acknowledgements The work was financed by a statutory activity subsidy from the Polish
Technology No. S40593/Z0309.
References
1. X. Sun et al., Anal. Bioanal. Chem., 406 (2014) 5359-5367.
2. L. Qin et al., Anal. Bioanal. Chem., 399 (2011) 3375-3385.
128
REMOVAL OF DIETHYL PHTHALATE BY pH-RESPONSIVE
MOLECULARLY IMPRINTED POLYMERS
Wrocław University of Technology, Faculty of Chemistry, 50-370 Wrocław,
Wybrzeże Wyspiańskiego 27, Poland
e-mail: joanna.wolska@pwr.edu.pl
Diethyl phthalate (DEP) is used as a plasticizer in a wide variety of consumer
products, including plastic packaging films, cosmetic formulations, and toiletries,
as well as in medical treatment tubing (1). As it is not chemically bound to
polymer chain it can migrate easily. Its release is expected to appear to various
aquifers or to soil due to leaching from landfills. Diethyl phthalate may also enter
the atmosphere through combustion of plastics and, to a lesser degree, by
volatilization (1). DEP is counted to the group of endocrine disruptors that
negatively affect the balance of the hormonal system.
This study presents preparation of pH-sensitive molecularly imprinted polymers
(PS-MIPs) that can be used for removal of DEP from solutions. Methyl
methacrylate (MMA), acrylic acid (AAc) and divinylbenzene (DVB) copolymers
were used to form polymer matrices synthesized in block and suspension
polymerizations. The block polymerization were carried out to find the best
monomer/solvent composition to use it in suspension polymerization. The
molecular recognition of PS-MIPs to diethyl 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
DEP removal was noted at pH=5 for material obtained by suspension
polymerization with monomers ratio AAc:MMA as 1:1, 70% of crosslinker, 3% of
footprint in hexane as porofor. The maximum diethyl phthalate capacity for this
PS-MIP was 110 mg DEP/g. The best desorption condition was reached at
pH=3, when more than 90% of diethyl phthalate was desorbed.
Acknowledgements The work was financed by a statutory activity subsidy from the Polish
Technology No. S40593/Z0309.
References
1. Concise International Chemical Assessment Document 52, DIETHYL PHTHALATRE, WHO,
Geneva, 2003, www.who.int/ipcs/publications/cicad/en/cicad52.pd
129
THE PROPERTIES OF POLYVINYLIMIDAZOLE-CLAY
COMPOSITES AND THEIR USE FOR REMOVAL OF REMAZOL
BLACK FROM WATER
Gulcemal Yildiz1, Filiz Senkal1, Nevin Oztekin1, Yuksel Orgun2
1
Istanbul Technical University, Faculty of Science and Letters, Department of
Chemistry, Istanbul, Turkey,
2 Istanbul Technical University, Faculty of Mines, Department of Geology,
Istanbul, Turkey
e-mail: gyildiz@itu.edu.tr
Organic coloring agents in waste water cause environmental pollution by mixing
surface waters and underground waters so that they can produce toxic
substances and carcinogens. Clays are used to remove organic pollutants
because of their wide surface area and high cation exchange capacity. Clays
are also used as fillers in polymer matrices due to their nanosize structure,
thermal and mechanical resistance, and high adsorbing properties (1).
Poly(vinyl imidazole) is a weak basic polyelectrolyte. Imidazole moieties have
ability to complex with divalent ions. When PVI is swollen in acid solutions, the
imidazole moieties become protonated and the gel behaves as a
polyelectrolyte. It is therefore, pH-responsive. Due to the tertiary amine groups,
PVI is a poly base and its positive charge density is pH dependent. It was
shown that PVI is significantly charged in acidic media, below pH 7. There has
been considerable interest in the characterization of the structure and properties
of the polymer–clay interface. PVI is interesting to work with because of its
relative simple synthesis adsorption properties (2,3).
In this study, PVI-clay (sodium bentonite and calcium bentonite) composites
were designed and characterized for the removal of Remazol Black (RB) that is
an anionic dye pollutant from water. The adsorption properties of PVI on
bentonite clay particles were investigated and then PVI-clay composites were
prepared at the optimum conditions for RB adsorption. X-ray diffractometry was
used to investigate the intercalation behaviors of polymer–clay composites.
Besides FTIR, SEM analyses in order to identify the interaction mechanisms
between PVI and bentonite in the composites.
Reference
1. Q. Li et al., J. Environ. Manage., 91 (2010) 1601-1611.
2. T. Roques-Carmes et al., J. Colloid Interface Sci., 245 (2002) 257-266.
3. T. Roques-Carmes et al., J. Colloid Interface Sci., 256 (2002) 273-283.
130
SELECTIVE REMOVAL OF GOLD FROM WASTE RINSE WATER
USING N-(DIETHYLTHIOPHOSPHORYL)-AZA[18]CROWN-6
IMPREGNATED AMBERLITE XAD-4 RESIN
Iwona Zawierucha, Cezary Kozłowski, Jolanta Kozłowska
Institute of Chemistry, Environment Protection and Biotechnology,
Jan Długosz University of Częstochowa, Armii Krajowej 13/15, 42-200
Częstochowa, Poland
e-mail: i.zawierucha@ajd.czest.pl
Precious metals are of great importance currently because of their widespread
applications in high-tech industries. Gold and palladium are especially
indispensable in the manufacture of mobile phones and computers. The
frequent replacement of these electronic devices causes the accumulation of
large amounts of electronic and electrical waste, offering an important recycling
opportunity for the secondary supply of precious metals. Accordingly, the
separation and recovery of gold from e-waste has attracted much interest (1).
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 (2). In SPE procedure, the choice
of appropriate adsorbent is a critical factor to obtain full recovery and high
enrichment factor (3). 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 (4). Novel types of resins incorporating macrocyclic ligands may be
the best choice for the removal of a variety of metal ions. The modification of
Amberlite XAD-4 with macrocyclic ligands results in the high capacity and
selectivity of the impregnated resins. The extractant is retained in the
micropores of an inert polymer without any chemical bonds onto the polymer
matrix and the properties of the impregnated extractant are responsible for the
adsorption of novel resin (5).
In this study batch sorption experiments were performed to evaluate the Au(III)
removal efficiency of N-(diethylthiophosphoryl)-aza[18]crown-6 impregnated
Amberlite (XAD-4) resin and sorbent selectivity. The values of correlation
coefficients (R2) indicated that the Langmuir isotherm model well described the
sorption equilibrium. The impregnated resin has been found efficient for
selective adsorption of Au(III) chloride complexes from waste rinse water. This
sorbent had high extraction ability towards gold ions and low ones for Pt(IV) and
Pd(II) chloride complexes. At initial concentration of 10 mg/l removal efficiencies
for Au(III), Pt(IV) and Pd(II) ions were 93%, 37% and 29%, respectively.
References
1. J. Yang et al., Carbohydr. Polym., 111 (2014) 768-774.
2. B.B. Adhikari et al., Chem. Eng. J., 172 (2011) 341-353.
3. M. Ghaedi et al., J. Hazard. Mater., 172 (2009) 802-808.
4. I. Zawierucha et al., Desalin. Water Treat., 52 (2014) 314-323.
5. I. Zawierucha et al., Waste Manage., 33 (2013) 2129-2136.
131
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141
AUTHORS INDEX
A
Antos D.
24
Çokgez İ.
B
Baczyńska M.
Bartnicki A.
Bastrzyk A.
Beltrami D.
Bildik F.
Bita B.I.
Bogacki M.B.
Bogdanov M.G.
Bok-Badura J.
Borisevich V.D.
Bryjak M.
Bunaciu A.A.
47
67
103
68
69
104
105
22
112
100
51
70
71
81
107
46
72
87
113
117
73
128
129
101
C
Canfarotta F.
Carvalho J.M.R.
Chagnes A.
Cierpiszewski R.
Ciopec M.
Coll T.M.
Cote G.
Cozae A.
Cyganowski P.
Czulak J.
142
78
116
22
31
74
75
32
123
124
47
22
31
101
76
77
78
79
D
Dartiguelongue A.
Davidescu C.M.
Diaconu I.
Dreisinger D.
Drzazga R.
Dudczak J.
Dudek G.
22
32
124
96
19
57
74
83
84
E
Erdem Y.
79
112
F
Feklistov D.Y.
Fortuny A.
Franczak J.
Furst W.
80
47
68
22
G
Gabor A.
Gajda B.
Gajewski P.
Gameiro M.L.F.
Gawdzik B.
Gęga J.
Gierszewska M.
Gnus M.
Górska M.
Guerreiro A.
32
70
81
51
107
116
27
103
38
82
83
84
127
26
78
85
H
Haddad M.
31
Hubicki Z.
88
89
115
126
127
Krasowska M.
Krzyżkowska A.
Kujawska M.
Kujawski J.
Kujawski P.
Kurchatov I.M.
32
116
L
I
Ianaşi C.
Ismael M.R.C.
J
Jakóbik-Kolon A.
Jakubiak-Marcinkowska A.
Jermakowicz-Bartkowiak D.
Jiang D.
Juskiewicz H.
86
87
63
76
77
113
111
K
Kalak T.
Kamar F.H.
Karim K.
Karoń K.
Kawakita H.
Keremedchieva R.
Kersten S.R.A.
Kołodziejska M.
Kołodyńska D.
Konieczny K.
Kowalczuk P.B.
Kozłowska J.
Kozłowski C.
Koźlecki T.
74
99
26
87
121
46
72
23
67
90
91
88
89
114
115
83
61
90
91
131
67
90
91
98
131
68
69
104
105
Laguntsov N.I.
Laskowska E.
Lech M.
Legan M.
Lupa L.
84
42
92
73
71
80
80
93
94
95
123
124
M
Maciejewski H.
Malysa K.
Markiewicz A.
Metran K.
Mendyk E.
Milewski A.K.
Mino T.
Mirea C.M.
Miron A.R.
Mitko K.
Modrogan C.
Molenda A.
Morisada S.
Murakami H.
N
Nechifor A.C.
Nechifor G.
Negrea A.
Negrea P.
Niecikowska A.
Nishihama S.
75
61
110
78
115
86
87
55
96
99
100
101
93
99
69
121
36
97
100
101
96
32
123
124
32
123
124
61
36
55
97
122
143
Nowik-Zając A.
98
O
Ohto K.
Omelchuk K.
Orbeci C.
Orgun Y.
Ostrowska-Czubenko J.
Otrembska P.
Oztekin N.
74
121
31
99
130
82
38
130
P
Pańczuk-Figura I.
Pascu D.-E.
Pascu M.
Piletska E.V.
Piletsky S.
Plackowski R.
Podkościelna B.
Polowczyk I.
Popa A.
Popescu M.C.
Pośpiech B.
Provost E.
Przewoźna M.
89
100
101
100
101
26
26
78
85
70
102
103
68
69
104
105
123
100
106
22
51
107
R
Radzymińska-Lenarcik E.
Regel-Rosocka M.
Reis M.T.A.
Reyhanitash E.
Ronka S.
144
108
109
125
42
47
67
110
116
116
23
63
111
Ruse E.
96
S
Sadowski Z.
Sofińska-Chmiel W.
Sastre A.M.
Schuur B.
Senkal B.F.
Serban E.A.
Siekierka A.
Skiba A.
Smirnov A.Yu.
Staszak K.
Strzelewicz A.
Sulaberidze G.A.
Svinyarov I.
Szczałba E.
Szczepańska G.
Szczepański P.
Şişmanoğlu T.
68
69
105
114
115
47
23
79
112
120
130
96
73
88
113
117
57
116
84
113
117
46
72
105
118
118
119
112
T
Tanaka S.
Tarnowska M.
Totu E.E.
Tórz A.
Traistaru G.A.
Trisca-Rusu C.
Trochimczuk A.W.
Trusek-Hołownia A.
Tsutsumi Y.
Turan G.T.
36
110
100
83
84
101
100
63
78
92
95
98
94
55
120
Turczyn R.
Turek M.
83
84
93
U
Ueda Y.
Ulatowska J.
Ulewicz M.
Umebayashi T.
Urbaniak W.
121
68
69
104
109
122
125
V
Voda R.
123
124
W
Whitcombe M.J.
Wieczorek D.
Wieszczycka K.
Witt K.
Wiśniewski M.
Wojciechowska A.
Wojciechowska P.
Wolska J.
Wódzki R.
Wójcik G.
26
57
116
125
42
47
67
116
75
128
129
119
126
127
Y
Yildiz G.
Yoshizuka K.
130
36
55
97
122
Z
Zawala J.
Zawierucha I.
Zdybał D.
Zeng S.
61
91
131
86
113
145

Conference Proceedings - 3rd International Conference on Methods

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