Wrocaw 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 Wrocawskiej

Wrocaw 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,

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Copyright by Oficyna Wydawnicza Politechniki Wrocawskiej, Wrocaw 2015

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IIIrd INTERNATIONAL CONFERENCE ON METHODS AND MATERIALS FOR SEPARATION PROCESSES

SEPARATION SCIENCE THEORY AND PRACTICE 2015

KARPACZ POLAND

6-10 SEPTEMBER 2015

organized by:

Faculty of Chemistry

Wrocaw University of Technology

INTERNATIONAL ADVISORY BOARD

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

ORGANIZING COMMITTEE

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

Address: Faculty of Chemistry

Wroclaw University of Technology Wybrzee Wyspiaskiego 27,

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

Fax: +4871 320 2152

5

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

D. Dreisinger 9:15 - 9:55 L3

B. Schuur 9:15 - 9:55 L5

M. Whitcombe 09:30

Bus departure for Wrocaw

9:55 - 10:35 L2

A. Chagnes 9:55 - 10:35 L4

D. Antos 9:55 - 10:35 L6

B. Gawdzik

10:35 - 10:55 S1

K. Omelchuk 10:35 - 10:55 S5

M. Regel-Rosocka

10:35 - 10:55 S9

S. Nishihama

10:55 - 11:20

Coffee Break 10:55 - 11:20

Coffee Break 10:55 - 11:20

Coffee Break

11:20 - 11:40 S2

A. Gabor 11:20 - 11:40 S6

M.G. Bogdanov 11:20 - 11:40 S10

K. Staszak

11:40 - 12:00 S3

K. Yoshizuka 11:40 - 12:00 S7

M. Baczyska 11:40 - 12:00 S11

P. Kowalczuk

12:00 - 12:20 S4

J. Gga 12:00 - 12:20 S8

M. Przewona 12:00 - 12:20 S12

A. Trochimczuk

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

Registration 15:00 - 17:00

Poster Session 14:00 - 18:30

Excursions

19:00 - 21:00

Welcome Reception

18:30 - 19:45

Dinner 19:30 - 01:30

Banquet

18:30 - 19:45

Dinner

6

7

I. LECTURES L1 David Dreisinger (University of British Columbia, Canada)

NEW PROSPECTS FOR ADVANCEMENT OF COPPER HYDROMETALLURGY FOR THE TREATMENT OF HIGH GRADE COPPER ORES AND CONCENTRATES

19

L2 A. Chagnes, A. Dartiguelongue, D. Beltrami, E. Provost, W. Furst, G. Cote (Chimie ParisTech - Institut de Recherche de Chimie Paris, France) NEW HIGHLIGHTS ON URANIUM RECOVERY FROM PHOSPHORIC ACID: FROM FUNDAMENTAL SCIENCE TO PROCESS

22

L3 E. Reyhanitash, S. R. A. Kersten, B. Schuur (University of Twente, The Netherlands) VOLATILE FATTY ACID RECOVERY FROM FERMENTATION BROTHS

23

L4 Dorota Antos (Rzeszw University of Technology, Poland) DOWNSTREAM PROCESS HOW TO CAPTURE A PROTEIN?

24

L5 Michael J. Whitcombe, Sergey A. Piletsky, Elena V. Pileska, 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

26

L6 Barbara Gawdzik (UMCS Lublin, Poland) ROLE OF POLYMERIC MATERIALS IN SEPARATION SCIENCE

27

8

II. SHORT LECTURES S1 K. Omelchuk, M. Haddad, G. Cote, A. Chagnes

NEW EXTRACTANTS FOR THE RECOVERY OF COBALT AND NICKEL ACIDIC CHLORIDE SOLUTIONS

31

S2 Andreea Gabor, Corneliu Mircea Davidescu, Adina Negrea, Mihaela Ciopec, Petru Negrea, Ctlin Ianai LANTHANUM REMOVAL FROM AQUEOUS SOLUTIONS USING FLORISIL IMPREGNATED WITH TETRABUTYLAMMONIUM DIHYDROGEN PHOSPHATE CANCELLED

32

S3 Kazuharu Yoshizuka, Shuhei Tanaka, Hironori Murakami, Syouhei Nishihama PRECIOUS METAL RECOVERY FROM THE WASTES USING ION EXCHANGE METHOD

36

S4 Jerzy Gga, Paulina Otrembska SEPARATION OF NICKEL(II) AND CADMIUM(II) IONS WITH ION-EXCHANGE AND MEMBRANE PROCESSES

38

S5 Magdalena Regel-Rosocka, Agnieszka Krzykowska, Maciej Winiewski REACTIVE EXTRACTION AS A METHOD FOR REMOVAL OF LOW MOLECULAR CARBOXYLIC ACIDS FROM FERMENTATION BROTH

42

S6 Milen G. Bogdanov, Rozalina Keremedchieva, Ivan Svinyarov IONIC LIQUIDS AS ALTERNATIVE SOLVENTS FOR SELECTIVE EXTRACTION OF SECONDARY METABOLITES FROM PLANT MATERIALS: A CASE STUDY

46

S7 M. Baczyska, M. Regel-Rosocka, T. M. Coll, A. Fortuny, A. M. Sastre, M. Winiewski PHOSPHONIUM IONIC LIQUIDS AS METAL ION CARRIERS THROUGH POLYMER INCLUSION MEMBRANES (PIM) AND SUPPORTED LIQUID MEMBRANES (SLM)

47

S8 Marta Przewona, Piotr Gajewski, Mariusz B. Bogacki INFLUENCE OF COMPOSITION OF MEMBRANE ON TRANSPORT OF SELECTED ORGANIC ACIDS THROUGH POLYMER INCLUSION MEMBRANE

51

S9 Syouhei Nishihama, Yasuhiro Tsutsumi, Takeru Mino, Kazuharu Yoshizuka NANOFILTRATION OF TETRAMETHYLAMMONIUM HYDROXIDE BY USING MFI-TYPE ZEOLITE COATED MEMBRANE

55

9

S10 Katarzyna Staszak, Roksana Drzazga, Daria Wieczorek MICELLAR-ENHANCED ULTRAFILTRATION FOR REMOVAL OF METAL IONS FROM AN AQUEOUS SOLUTION CANCELLED

57

S11

Przemyslaw B. Kowalczuk, Jan Zawala, Anna Niecikowska, Kazimierz Malysa FLOTATION, HYDROPHOBICITY AND BUBBLE ATTACHMENT TO THE QUARTZ SURFACE IN THE PRESENCE OF HEXYLAMINE

61

S12 Andrzej W. Trochimczuk, Anna Jakubiak-Marcinkowska, Sylwia Ronka NEW, POLAR POLYMERIC ADSORBENTS FOR THE IMPROVEMENT OF PHENOLS SORPTION

63

10

III. POSTERS

P1 Monika Baczyska, Marta Koodziejska, Magdalena Regel-

Rosocka, Cezary Kozowski, Maciej Winiewski COMPARISION OF TRANSPORT OF ZINC AND IRON IONS THROUGH POLYMER INCLUSION MEMBRANES (PIM) IN SANDWICH TYPE MODULE AND GLASS PERMEATION CELL

67

P2 Justyna Ulatowska, Izabela Polowczyk, Anna Bastrzyk, Tomasz Kolecki, Joanna Franczak and Zygmunt Sadowski SORPTION OF HEAVY METAL IONS BY FLY ASH: EXPERIMENTAL AND MODELING STUDIES

68

P3 Anna Bastrzyk, Izabela Polowczyk, Aleksandra Molenda, Tomasz Kolecki, Justyna Ulatowska and Zygmunt Sadowski ADSORPTION OF Cu(II) AND Ni(II) IONS ONTO GREEN TEA LEAVES

69

P4 Bernadeta Gajda, Radosaw Plackowski, Mariusz B. Bogacki FACILITATED TRANSPORT OF METAL IONS THROUGH POLYMER INCLUSION MEMBRANES CONTAINING 1-ALKYL-1,2,4-TRIAZOLES AS A CARRIERS

70

P5 Mariusz B. Bogacki, Piotr Kujawski THEORETICAL STUDIES ON TRI-OCTYLOAMINE (TOA), TRI-n-BUTYL PHOSPHATE (TBP) AND 1-DECYL-IMIDAZOLE (IMID10) USING MOLECULAR DYNAMICS SIMULATIONS

71

P6 Rozalina Keremedchieva, Ivan Svinyarov, Milen G. Bogdanov IONIC LIQUID-ASSISTED EXTRACTION AS A SAMPLE PREPARATION TECHNIQUE FOR HPLC DETERMINATION OF BIOLOGICALLY ACTIVE ALKALOID GALANTAMINE IN LEUCOJUM AESTIVUM L. (SUMMER SNOWFLAKE)

72

P7 Marek Bryjak, Anna Siekierka, Jan Kujawski CAPACITIVE DEIONIZATION METHOD FOR EXTRACTION OF LITHIUM

73

P8 Ryszard Cierpiszewski, Joanna Dudczak, Tomasz Kalak, Keisuke Ohto PAPRIKA WASTE AS A BIOSORBENT FOR REMOVING HEAVY METALS FROM AQUEOUS SOLUTIONS

74

P9 Ryszard Cierpiszewski, Patrycja Wojciechowska, Hieronim Maciejewski ADSORPTION OF Cu(II) FROM AQUEOUS SOLUTIONS ON GELATIN-SILOXANE HYBRID MATERIALS

75

11

P10 Piotr Cyganowski, Dorota Jermakowicz-Bartkowiak NEW CORE-SHELL TYPE POLYMERIC SUPPORTS BASED ON THE AMBERLITE XAD-4 ADSORBENT

76

P11 Dorota Jermakowicz-Bartkowiak, Piotr Cyganowski ECOFRIENDLY LOW-COST NATURAL BIOSORBENTS TOWARDS RECOVERY OF GOLD

77

P12 Joanna Czulak, Antonio Guerreiro, Karima Metran, Francesco Canfarotta, Andrzej Trochimczuk, Sergey Piletsky CROSS-LINKED HORSERADISH PEROXIDASE BY MODIFIED BIO-IMPRINTING PROCESS FOR IMMUNOASSAYS

78

P13 Yavuz Erdem, rem okgez, B. Filiz enkal A NEW POLYMERIC SORBENT FOR REMOVAL OF MERCURY IONS FROM AQUEOUS SOLUTIONS

79

P14 D. Y. Feklistov, I. M. Kurchatov, N. I. Laguntsov POSSIBLE MECHANISMS OF THE WATER TREATMENT WITH ALUMINO-SILICIC REAGENT

80

P15 Bernadeta Gajda, Mariusz B. Bogacki INFLUENCE OF TEMPERATURE ON TRANSPORT OF Ni(II), Co(II), Cd(II) AND Zn(II) THROUGH POLYMER INCLUSION MEMBRANES

81

P16 Magdalena Gierszewska, Jadwiga Ostrowska-Czubenko SEPARATION OF WATER/ALCOHOL MIXTURES WITH CHITOSAN MEMBRANES

82

P17 Magorzata Gnus, Gabriela Dudek, Roman Turczyn, Artur Trz, Krystyna Konieczny TRANSPORT PROPERTIES OF CHITOSAN AND ALGINIC MEMBRANES APPLIED FOR PERVAPORATIVE DEHYDRATION OF ETHANOL

83

P18 Gabriela Dudek, Magorzata Gnus, Anna Strzelewicz, Monika, Krasowska, Roman Turczyn, Artur Trz PERMEATION OF ETHANOL AND WATER VAPOURS THROUGH CHITOSAN MEMBRANES WITH FERROFERIC OXIDE PARTICLES

84

P19 Antonio Guerreiro and Sergey Piletsky AUTOMATED SYNTHESIS OF MOLECULARLY IMPRINTED POLYMER NANOPARTICLES

85

P20 Dominik Zdyba, Andrzej K. Milewski, Agata Jakbik-Kolon PMMA-BASED SORBENTS FOR ZINC REMOVAL

86

12

P21 A. Jakbik-Kolon, A. K. Milewski, K. Karo, J. Bok-Badura NEW, HYBRID PECTIN-BASED BIOSORBENTS

87

P22 Dorota Koodyska, Alicja Skiba, Zbigniew Hubicki HYDROGELS APPLICATION IN HEAVY METAL COMPLEXES REMOVAL

88

P23 Dorota Koodyska, Irmina Paczuk-Figura, Zbigniew Hubicki REMOVAL OF GLDA COMPLEXES WITH HEAVY METALS ON N-METHYL-D-GLUCAMINE RESIN

89

P24 Marta Koodziejska, Cezary Kozowski, Jolanta Kozowska TRANSPORT OF GOLD ACROSS POLYMER INCLUSION MEMBRANES CONTAINING N-(DIETHYLTHIOPHOSPHORYL)-AZA[18]CROWN-6

90

P25 Marta Koodziejska, Cezary Kozowski, Jolanta Kozowska, Iwona Zawierucha RESORCINARENES AS ION CARRIERS OF Au(III), Pt(IV), Pd(II) IN TRANSPORT ACROSS IMMOBILIZED MEMBRANES

91

P26 Magorzata Kujawska, Andrzej W. Trochimczuk MOLECULARLY IMPRINTED POLYMERIC ADSORBENT FOR -BLOCKERS REMOVAL SYNTHESIZED USING FUNCTIONALIZED MSU-F SILICA AS A SACRIFICIAL TEMPLATE

92

P27 Ewa Laskowska, Krzysztof Mitko, Marian Turek MINE WATER NANOFILTRATION SEPARATION OF MONO AND POLYVALENT IONS

93

P28 Magdalena Lech, Anna Trusek-Holownia SEPARATION OF WHEY COMPOUNDS IN PRESSURE MEMBRANE PROCESSES: PROTOCOL FOR THE ORGANIC COMPOUNDS FRACTIONATION TO THEIR FURTHER USE

94

P29 Magdalena Legan, Andrzej W. Trochimczuk FUNCTIONALIZED POLY(HIPE) AS A MONOLITH ADSORBENT FOR ION EXCHANGE PROCESS

95

P30 C. M. Mirea, I. Diaconu, E. A. Serban, E. Ruse, G. Nechifor COMPETITIVE TRANSPORT OF Fe(III) AND Mn(II) IONS THROUGH BULK LIQUID MEMBRANES

96

P31 Hironori Murakami, Syouhei Nishihama, Kazuharu Yoshizuka SELECTIVE RECOVERY OF Dy FROM WASTE Nd MAGNET USING COATED SOLVENT IMPREGNATED RESIN

97

P32 Anna Nowik-Zajc, Cezary Kozowski, Andrzej Trochimczuk SELECTIVE TRANSPORT OF Ag(I) AND Cu(II) ACROSS PLASTICIZED MEMBRANES WITH CALIX[4]PYRROLES

98

13

P33 Cristina Orbeci, Cristina Modrogan, Alexandra Raluca Miron,

Firas Hashim Kamar REMOVAL OF HEAVY METAL IONS THROUGH ION EXCHANGE

99

P34 Daniela-E. Pascu, Alexandra R. Miron, Mihaela Pascu (Neagu), 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

100

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 OF BIOLOGICALLY ACTIVE EXTRACTS

101

P36 Beata Podkocielna SYNTHESIS AND PHYSICO-CHEMICAL PROPERTIES OF GMA TERPOLYMERS FOR ENZYMES IMMOBILIZATION

102

P37 Beata Podkocielna, Andrzej Bartnicki, Barbara Gawdzik SYNTHESIS, STRUCTURE AND PROPERTIES OF THE NEW MICROSPHERES WITH LIGNIN UNITS

103

P38 Izabela Polowczyk, Anna Bastrzyk, Tomasz Kolecki HYDROPHOBIC AGGREGATION OF FINE CALCIUM CARBONATE PARTICLES IN AQUEOUS SOLUTION

104

P39 Justyna Ulatowska, Izabela Polowczyk, Tomasz Kolecki, Anna Bastrzyk, Ewelina Szczaba, and Zygmunt Sadowski INFLUENCE OF pH ON ARSENIC(III) REMOVAL BY FLY ASH

105

P40 Beata Popiech EVALUATION OF Pd(II) TRANSPORT FROM AQUEOUS CHLORIDE SOLUTIONS ACROSS POLYMER INCLUSION MEMBRANES WITH IONIC LIQUIDS

106

P41 Piotr Gajewski, Marta Przewona, Mariusz B. Bogacki FACILITATED TRANSPORT OF SELECTED ORGANIC ACIDS THROUGH POLYMER INCLUSION MEMBRANES CONTAINING 1-ALKYL-1,2,4 TRIAZOLES AS CARRIERS

107

P42 Elbieta Radzymiska-Lenarcik EXAMINATION OF THE FORMATION OF Cd(II) COMPLEXES WITH 1-ALKYLIMIDAZOLE BY THE LIQUID-LIQUID PARTITION METHOD

108

14

P43 Elbieta Radzymiska-Lenarcik, Magorzata Ulewicz

APPLICATION OF POLYMER MEMBRANES WITH 1-ALKYL-4-METHYLIMIDAZOLE FOR RECOVERY OF ZINC FROM WASTE

109

P44 Magdalena Regel-Rosocka, Marta Tarnowska, Agnieszka Markiewicz REMOVAL OF Zn(II), Cu(II), Co(II), Ni(II) FROM CHLORIDE AND SULFATE SOLUTIONS WITH MIXTURES OF ACIDIC AND BASIC EXTRACTANTS

110

P45 Sylwia Ronka, Honorata Juskiewicz FIXED-BED ADSORPTION OF TRIAZINES ON SPECIFIC POLYMERIC SORBENT

111

P46 Fatih Bildik, Bahire Filiz Senkal, Tuba imanolu, Erdem Yavuz PREPARATION OF POLY (2-ACRYLAMIDO-2-METHYLPROPANE SULFONIC ACID) (AMPS) GRAFTED ONTO CROSSLINKED POLY(VINYLBENZYL CHLORIDE) RESIN FOR REMOVAL OF ATRAZINE FROM WATER

112

P47 A. Yu. Smirnov, G. A. Sulaberidze, V. D. Borisevich, S. Zeng, D. Jiang TRANSIENT PROCESSES IN MODEL CASCADES

113

P48 Weronika Sofiska-Chmiel, Dorota Koodyska PUROLITE S 940 AND PURLITE S 950 IN HEAVY METAL IONS REMOVAL FROM ACIDIC STREAMS

114

P49 Weronika Sofiska-Chmiel, Dorota Koodyska, Ewaryst Mendyk and Zbigniew Hubicki REMOVAL OF Cu(II) USING ION EXCHANGE RESINS WITH ANIONOPHOSHONIC FUNCTIONAL GROUPS

115

P50 Katarzyna Staszak, Karolina Wieszczyka, Magdalena Regel-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)

116

P51 V. D. Borisevich, A. Yu. Smirnov, G. A. Sulaberidze ON THE SEPARATIVE POTENTIAL (VALUE FUNCTION) FOR SEPARATION OF MULTICOMPONENT MIXTURES: STATUS OF THE PROBLEM

117

P52 Piotr Szczepaski, Grayna Szczepaska THE RESPONSE SURFACE ANALYSIS FOR ESTIMATION OF THE MASS TRANSFER COEFFICIENT IN PERTRACTION

118

15

P53 Piotr Szczepaski, Romuald Wdzki TRANSPORT AND SEPARATION OF PHENOL AND p-NITROPHENOL IN AN AGITATED BULK LIQUID MEMBRANE SYSTEM. EXPERIMENTAL AND THEORETICAL STUDY BY NETWORK ANALYSIS

119

P54 Gulcin Torunoglu Turan, B. Filiz Senkal MODIFICATION OF POLY(GLYCIDYL METHACRYLATE) GRAFTED ONTO CROSSLINKED POLY(3-CHLORO-2-HYDROXYPROPYL METHACRYLATE-METHYL METHACRYLATE (MMA)-ETHYLENE GLYCOLE DIMETHACRYLATE (EGDMA)) WITH AMINO-BIS-(CIS-PROPAN 2,3 DIOL) FUNCTIONS FOR REMOVAL OF BORON FROM WATER

120

P55 Yuki Ueda, Shintaro Morisada, Hidetaka Kawakita, Keisuke Ohto SOLVENT EXTRACTION OF PRECIOUS METAL IONS WITH TRIMETHYLACETAMIDE TYPE OF TRIDENT MOLECULE

121

P56 Toshiyuki Umebayashi, Syouhei Nishihama, Kazuharu Yoshizuka OXIDATIVE ADSORPTION OF ARSENIC WITH N-METHYL GLUCAMINE BASED ADSORBENT AND MANGANESE DIOXIDE

122

P57 Lavinia Lupa, Adriana Popa, Raluca Voda, Petru Negrea, Mihaela Ciopec, Adina Negrea STRONTIUM ADSORPTION ON IONIC LIQUID IMPREGNATED FLORISIL. FIXED-BED COLUMN STUDIES

123

P58 Raluca Vod, Lavinia Lupa, Adina Negrea, Mihaela Ciopec, Petru Negrea, Corneliu M. Davidescu THE DEVELOPMENT OF A NEW EFFICIENT ADSORBENT FOR THE REMOVAL OF METHYLENE BLUE

124

P59 Katarzyna Witt, Elbieta Radzymiska-Lenarcik, Wodzimierz Urbaniak APPLICATION OF -DIKETONES DERIVATIVES FOR SELECTIVE SEPARATION OF COPPER IONS IN THE TRANSPORT PROCESS ACROSS A POLYMERIC INCLUSION MEMBRANE

125

P60 Grzegorz Wjcik, Zbigniew Hubicki INVESTIGATION OF CHROMIUM (III AND VI) IONS SORPTION ON WEAKLY BASIC ANION EXCHANGER

126

P61 Grzegorz Wjcik, Zbigniew Hubicki, Magdalena Grska NEW SOLVENT IMPREGNATED RESIN AMBERLITE XAD 7 HP FOR RECOVERY OF GOLD(III) IONS FROM METALLIC SECONDARY SOURCES

127

16

P62 Joanna Wolska, Marek Bryjak THERMORESPONSIVE MOLECULARLY IMPRINTED POLYMER FOR FAST SORPTION AND DESORPTION OF DIETHYL PHTHALATE

128

P63 Joanna Wolska, Marek Bryjak REMOVAL OF DIETHYL PHTHALATE BY pH-RESPONSIVE MOLECULARLY IMPRINTED POLYMERS

129

P64 Gulcemal Yildiz, Filiz Senkal, Nevin Oztekin, Yuksel Orgun THE PROPERTIES OF POLYVINYLIMIDAZOLE-CLAY COMPOSITES AND THEIR USE FOR REMOVAL OF REMAZOL BLACK FROM WATER

130

P65 Iwona Zawierucha, Cezary Kozowski, Jolanta Kozowska SELECTIVE REMOVAL OF GOLD FROM WASTE RINSE WATER USING N-(DIETHYLTHIOPHOSPHORYL)-AZA[18]CROWN-6 IMPREGNATED AMBERLITE XAD-4 RESIN

131

NOTES 132

AUTHORS INDEX 142

I. LECTURES

19

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.

Reagents

Wash Final

Water Residue

Raffinate

Bleed

Copper Cathode

Gold and Silver

Copper Leaching

S/L Separation

Copper SX-EW

Precious Metal

Recovery

Copper Ore or Concentrate

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 m Use high temperature (+200C) aggressive conditions

20

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)

Process Status Temp. Press. Ultrafine Chloride Surfactant Special

(C) (atm) Grind

Considerations

Activox Process D 110 12 Yes No No Albion Process P 85 1 Yes No No AAC- UBC P/C 150 12 Yes No Yes Bactech/Mintek

Low T Bioleach P 35 1 Yes No No

BIOCOP C 80 1 No No No Thermo-philes

CESL Process C 150 12 No Yes Yes Cobre Las Cruces C 90 1 No No No Chalcocite

Dynatec P 150 12 No No Yes Coal+

Recycle

Galvanox P 80 1 No No No Galvanic

Mt. Gordon C 90 8 No No No Chalcocite

PLATSOL P 225 32 No Yes No

Sepon Copper C 80 Cu 1 No No No Chalcocite

220 FeS2 32 No No No Total Press. Ox. C 225 32 No No No

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

21

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-/Br- Co-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.

22

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.

23

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. Ycel and U. Gndz, 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.

24

DOWNSTREAM PROCESS HOW TO CAPTURE A PROTEIN?

Dorota Antos

Rzeszw University of Technology, Faculty of Chemistry, Department of Chemical and Process Engineering,

Powstacw Warszawy 6 Ave., 35-959 Rzeszw, 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.

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.

Antibodies

25

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. Ry et al., Eng. Life Sci., 15 (2015) 140-151. 4. S. Ry et al., Chem. Eng. Sci., 130 (2015) 290-300.

26

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.

27

ROLE OF POLYMERIC MATERIALS IN SEPARATION SCIENCE

Barbara Gawdzik

Department of Polymer Chemistry, Maria Curie Skodowska 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.

II. SHORT LECTURES

31

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.

32

LANTHANUM REMOVAL FROM AQUEOUS SOLUTIONS USING FLORISIL IMPREGNATED WITH TETRABUTYLAMMONIUM

DIHYDROGEN PHOSPHATE

Andreea Gabor1, Corneliu Mircea Davidescu1, Adina Negrea1, Mihaela Ciopec1, Petru Negrea1, Ctlin Ianai2

1 Politehnica University Timioara, Faculty of Industrial Chemistry and

Environmental Engineering, Victoriei Square Nr. 2, 300006 Timioara, Romnia 2 Institute of Chemistry Timioara of Romanian Academy, Romanian Academy,

Blv. Mihai Viteazul no. 24, 300223 Timioara, Romnia e-mail: emeline_gabor@yahoo.com

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 bio-accumulation 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

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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 4000400 cm-1 and BET surface area analysis using a Nova 1200 E Quanta Chrom. 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 cm-1 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).

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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

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

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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.

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. Karada et al., Water Sci. Technol., 69 (2014) 312-319.

12. R. Kala et al., Anal. Chim. Acta, 518 (2004) 143-150.

13. Y. Andrs 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. . elik 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.

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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 80C 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 Mn Zn

Leaching amount (mg/g) 12.8 6.77 > 1.96 2.17 0.0584 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

37

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.

Time ( h )

0 5 10 15 20 25

Adsorp

tion y

ield

( %

)

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Zn

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0 200 400 600 800

[ A

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)

0

5

10

0 50 1000

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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 WA-21 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.

B. V. [ - ]

0 2 4 6 8

[ P

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]

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10000

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600

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Thiourea / HCl H2SO4

(b) Elution

Fig. 3 Elution curves of Pd, Pt and Rh from DHS impregnated resin; Eluent: 0.1

mol/L thiourea - 1 mol/L HCl

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.

38

SEPARATION OF NICKEL(II) AND CADMIUM(II) IONS WITH ION-EXCHANGE AND MEMBRANE PROCESSES

Jerzy Gga, Paulina Otrembska

Czstochowa University of Technology, Department of Chemistry,

19 Armii Krajowej Str., 42-200 Czstochowa, 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 8/3-hydrate 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 m and diameter 47 mm were used. These filters were soaked in 1 M

39

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). 3. Results and discussion 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.

0 10 20 30 40 50 60

0.0

0.2

0.4

0.6

0.8

1.0

c/c

0

(b)(a)

Ni(II)

Cd(II)

t, min

0 10 20 30 40 50 60

0.0

0.2

0.4

0.6

0.8

1.0

c/c

0

Ni(II)

Cd(II)

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

40

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.

0,0

0,2

0,4

0,6

0,8

1,0

Metal ions init. conc.:

0,1 M

0,01 M

0,001 M

0,0001 M

c/c

0

Ni(II)

0 1 2 3 4 5

0,0

0,2

0,4

0,6

0,8

1,0

(a)

c/c

0

Cd(II)

pH

0,0

0,2

0,4

0,6

0,8

1,0

Metal ions init. conc.:

0,1 M

0,01 M

0,001 M

0,0001 M

c/c

0

Ni(II)

0 1 2 3 4 5

0,0

0,2

0,4

0,6

0,8

1,0

(b)

c/c

0

Cd(II)

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-2-ethylhexylphosphoric 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.

41

0 5 10 15 20 250.0

0.2

0.4

0.6

0.8

1.0

(c)

(b)(a)

Ni(II)

Cd(II)

t, h

c/c

0

0 5 10 15 20 250.0

0.2

0.4

0.6

0.8

1.0

Ni(II)

Cd(II)

c/c

0

t, h

0 5 10 15 20 250.0

0.2

0.4

0.6

0.8

1.0

Ni(II)

Cd(II)

c/c

0

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, 111112 (2012) 1-9.

42

REACTIVE EXTRACTION AS A METHOD FOR REMOVAL OF LOW MOLECULAR CARBOXYLIC ACIDS

FROM FERMENTATION BROTH

Magdalena Regel-Rosocka, Agnieszka Krzykowska, Maciej Winiewski

Pozna University of Technology, Faculty of Chemical Technology, Institute of

Chemical Technology and Engineering, Berdychowo St. 4, 60-965 Pozna, 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 20C 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.

43

Table 1. Declared composition of the fermentation broth

Component Content declared, g/dm3 Real broth, g/dm3

Propane-1,3-diol (PD) 32 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: )SAH(nSAH n22 . 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.

For Ac Lac Suc Gl PD0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

30

Component

caq,

g/d

m3

0.1 M Cyanex 923

0.4 M Cyanex 923

before extraction

For Ac Lac Suc Gl PD

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Component

co,

g/d

m3

0.1 M Cyanex 923

0.4 M Cyanex 923

a) 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

44

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

0.1 M Cyanex 923 0.4 M Cyanex 923

But For Ac Lac But For Ac Lac

I stage of extraction

3.73 0.48 0.39 0.16 20.1 2.74 1.28 0.46

II stage of extraction

2.78 0.35 0.25 0.18 - 4.36 2.64 0.85

III stage of extraction

55.1 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.

For Lac Ac0

10

20

30

40

50

60

% E

Component

two-component solution

model broth

real broth

0.1 M Cyanex 923

0.4 M Cyanex 923

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

45

Comparison of extraction of the carboxylic acids from various solutions, i.e. two-component (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 two-component 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.01.01.02-00-074/09)

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. Winiewski, 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.

46

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 solidliquid 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 solidliquid 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 post-treatment 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. Technol., (2015)

doi:10.1016/j.seppur.2015.02.003

47

PHOSPHONIUM IONIC LIQUIDS AS METAL ION CARRIERS THROUGH POLYMER INCLUSION MEMBRANES (PIM) AND

SUPPORTED LIQUID MEMBRANES (SLM)

M. Baczyska1, M. Regel-Rosocka1, T. M. Coll2, A. Fortuny2, A. M. Sastre2,

M. Winiewski1

1 Pozna Institute of Technology, Institute of Chemical Technology and

Engineering, Berdychowo St.4, 60-965 Pozna, Poland, 2 Universitat Politcnica 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 liquid-liquid 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), o-nitrophenyl 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(2,4,4-trimethylpentyl)phosphinate (Cyphos IL 104) supplied by Cytec Industry Inc. (USA) were applied as carriers for metal ions in PIMs. The aqueous feed phase containing 1.510-3 M (Zn) and 1.810-3 M Fe (0.1 g/dm3), 0.58 M HCl, 5 M Cl-

(NaCl was used to obtain constant chloride content). 1 M H2SO4 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 m, porosity 75%, thickness 125 m) was used as

48

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:

ktc

cln

0

(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/m2s)

00 ckA

VJ (2)

where V is the volume of both aqueous phases, A is the effective membrane area,

- Permeability coefficient (P, m/s)

kA

VP (3)

Results and discussion Figure 1 shows the mass transport of Zn(II), Fe(II) and Fe(III) ions across SLM and PIM.

49

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 2110-6, mol/sm2), in the case of Zn(II) transport through PIM containing the same carrier the value of initial flux is equal to 1410-6, mol/sm2. Almost no transport of Zn(II), Fe(II) and Fe(III) is noted with SLM containing Cyphos IL 104 (very low values of J0). 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:

%c

ccE 100

0

0

(4)

%c

cRF s 100

0

(5)

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.

50

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.

51

INFLUENCE OF COMPOSITION OF MEMBRANE ON TRANSPORT OF SELECTED ORGANIC ACIDS THROUGH

POLYMER INCLUSION MEMBRANE

Marta Przewona, Piotr Gajewski, Mariusz B. Bogacki

Pozna University of Technology, Institute of Chemical Technology and

Engineering, Berdychowo 4, 60-965 Pozna, 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.

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Fig. 1. Experimental apparatus diagram: 1chamber with receiving phase, 2chamber

with feeding phase, 3polymer inclusion membrane, 4stirrers, 5electrode, 6temperature 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:

tPV

A

C

C

0

21ln

2

1, (1)

where, C0 - the initial concentration of the organic acid [mol/dm3], C - concentration of organic acid in the receiving phase at time t [mol/dm3], V