I THANK THE ORGANIZERS TO GIVE ME THE OPPORTUNITY TO ATTEND THIS VERY INTERESTING SYMPOSIUM AND I APPRECIATE THEIR EFFORTS

Transcription

1 I THANK THE ORGANIZERS TO GIVE ME THE OPPORTUNITY TO ATTEND THIS VERY INTERESTING SYMPOSIUM AND I APPRECIATE THEIR EFFORTS TO BRING TOGETHER SPECIALISTS IN THIS EXCITING FIELD!

2 NOVEL BIPOLAR RESINS SYNTHESIS AND THEIR RETENTION PROPERTIES OF INORGANIC SALTS VIOLETA NEAGU, CORNELIA LUCA, SILVIA VASILIU PETRU PONI INSTITUTE OF MACROMOLECULAR EMISTRY, IASI ROMANIA

3 IASI

4 CONTENT I. SYNTHESIS OF THE BIPOLAR ION EXANGERS BASED ON THE PYRIDINE CROSSLINKED COPOLYMER II. RETENTION STUDY OF THE HEAVY METALS ON THE PYRIDINE BIPOLAR RESINS

5 ION EXANGER WHAT IS IT? B B B B A A B A A A B B A A B B B B Ion exchangers are solid polyelectrolytes which can exchange their mobile ions for ions of the same charge from the sorrounding medium. The ion exchangers are tools for the established procedures and technologies of the ion exchange.

6 BENEFITS OF THE ION EXANGE PROCESS: - highly efficient process, > 99.9% removal of desired ions - very high water recovery, > 97% - predictable performance - ability to remove selective impurities - re-use after regeneration up to several cycles APPLICATIONS OF ION EXANGERS: WATER TREATMENT HYDROMETALLURGY FOOD INDUSTRY EMICAL PROCESS INDUSTRY BIOEMISTRY AND BIOTENOLOGY, PHARMACEUTICALS MEDICINE, POLLUTION CONTROL, ANALYTICAL EMISTRY..

7 HOW DOES IT WORK? ORGANIC INORGANIC NATURAL SYNTHETIC Polymerization Polycondensation GEL TYPE ISOPOROUS TYPE MACROPOROUS TYPE

8 ION EXANGE MATERIALS Beads Films Fibers Fabrics Tubes Foams Plates BEADS OR GRANULES THERE ARE QUITE A NUMBER OF DIFFERENT TYPES OF ION EXANGERS BUT THOSE BASED ON BEADS OR GRANULES ORGANIC POLYMERS BECOME THE MOST IMPORTANT

9 CATION EXANGER Weak Acid: -COOH carboxylic acid -C 6 H 5 -OH phenolic hydroxyl Strong Acid: -C 6 H 5 SO 3 H aryl sulfonic ANION EXANGER: Weak Base: -NH 2 primary amine -NHR secondary amine -NR 2 tertiary amine Strong Base: >N < quaternary ammonium >P < phosphonium -S < sulfonium BIPOLAR EXANGERS: mixture of acid and base groups Amphoteric Zwitterionic

10 ZWITTERIONIC EXANGERS ION EXANGERS WITH BETAINE STRUCTURES ( ) n R N R X _ ( N ) n X _ Where X - = carboxylate = sulfonate = phosphate/ phosphonate/ phosphinate CROSSLINKED POLYCARBOXYBETAINES CROSSLINKED POLYSULFOBETAINES CROSSLINKED POLYPHOSPHOBETAINES

11 SYNTHESIS OF CROSSLINKED POLYCARBOXYBETAINES 1. Synthesis of 4-vinylpyridine : divinylbenzene copolymers N N 2. Synthesis of polycarboxybetaines Nucleophilic substitution 2 N 2 Nucleophilic addition 2 2 _ 2. Cl COONa =-COOH 2 2 N _ COO 2 2 _ 2. N _ 2. N 2 COO _ 2.

12 FT-IR characterization of the bipolar pyridine resins 4-VP : DVB A N DB = 90% B N COO - DB = 94% C N COO - Chemical stability of the bipolar pyridine resins HCl Na 2 CO 3

13 The most polluting sources are the city sewage and industrial waste discharged into the rivers. TODAY Roadways and automobiles are considered to be one of the largest sources of heavy metals COMMON METALS IN ROAD RUNOFF Lead: leaded gasoline, tire wear, lubricating oil and grease, bearing wear Zinc: tire wear, motor oil, grease, brake emissions, corrosion of galvanized parts Iron: auto body rust, engine parts Copper: bearing wear, engine parts, brake emissions Cadmium: tire wear, fuel burning, batteries Chromium: air conditioning coolants, engine parts, brake emissions Nickel: diesel fuel and gasoline, lubricating oil, brake emissions Aluminum: auto body corrosion

14 METAL RETENTION STUDY ON THE CROSSLINKED POLYCARBOXYBETAINES 1. Thermodynamic study Cu Cd Co (NO 3- ) meq NO 3- /g meq NO 3- /g Q (meq/g) meq NO 3- /g 0.42 meq NO 3- /g Q (meq/g) meq NO 3- /g 0.59 meq NO 3- /g C (mg/l) C (mg/l)

15 Cd(II) Cu(II) Q (meq/g) C (mg/l) Q (meq/g) C (mg/l) Co(II) Q (meq/g) C (mg/l)

16 Recovery factor of the studied heavy metals 120 Cd(II) 120 Cu(II) R (%) R (%) a (g) a (g) Co(II) R (%) a (g)

17 Retention of Cu(II) from various salts Q (meq/g dry resin) Cu(NO3)2 CuCl2 CuSO4 Cu(3COO)2 copper salt

18 2. Kinetic study Q (meq/g) Q (meq/g) Cd(II) Cu(II) Co(II) Time (h) Time (h)

19 - OOC N N N Inorganic salts N COO - COO- COO- A - C Inter- chain and intra - groups bindings N N A - N A - - OOC COO - C N A - COO - C COO - C

20 N N COO - COO - COO - COO - Inorganic salts N N A - C Intra- group bindings N A - N A - COO - C COO - C COO - C COO - C A - N A - N

21 CONCLUSIONS CROSSLINKED POLYCARBOXYBETAINES BASED ON 4-VINYLPYRIDINE : DIVINYLBENZENE N N COO - COO - BIPOLAR ION EXANGERS CONCOMITENTLY BIND THE CATIONS AND ANIONS (A - C ) FROM INORGANIC SALTS

22 THANK YOU FOR YOUR ATTENTION!