DEVELOPMENT OF FLOCCULANTS USING HEALTHY-FRIENDLY PROCESSES A. Lourenço 1,2 , J. Arnold 2 and M. G. Rasteiro 1, * 1 Chemical Engineering Department, University of Coimbra, Rua Sílvio Lima, 3030-790 Coimbra, Portugal. 2 Aqua+Tech Specialities SA, 1237 Avully, Geneva, Switzerland. [email protected], [email protected]* The main objective of this work is the development of new flocculants medium using healthy-friendly ingredients in their synthesis. A new polymerization medium has been tested with a well-known copolymer for water treatment formulations, consisting of cationic quaternary ammonium and acrylamide monomers. As these polymers are produced in inverse-emulsion, alternative continuous phases can be employed including purified mixtures of liquid saturated hydrocarbons, with higher boiling point. Those are of high purity due to their manufacturing process being free of the toxic polycyclic aromatics and heavy metals. Polyacrylamide-co-dimethylaminoethyl acrylate (AAm_AETAC) was synthesized with three different oils and three different polymer compositions, in order to evaluate if it is possible to produce copolymers with controlled properties and different charge densities using the previous mentioned healthy-friendly oils. The results showed that these oils are suitable to produce copolymers with high molecular weight and having different charge densities, keeping the emulsion stability unchanged. In addition, a further step could be achieved by partially replacing the ethoxylated surfactant. ACKNOWLEDGEMENTS The authors would like to thank for financial support from Marie Curie Actions – European Industrial Doctorate (EID), through Grant agreement FP7-PEOPLE-2013-ITN-604825, and from Portuguese Foundation for Science and Technology (Pest/C/EQB/UI0102/2013). Also, to Dr. David Hunkeler and Aqua+Tech Specialities SA (Switzerland). REFERENCES M. G. Rasteiro, F. A. P. Garcia, P. J. Ferreira, E. Antunes, D. Hunkeler and C. Wandrey, J. Appl. Polym. Sci. 2010, 116, p. 3603–3612. J. Hernandez Barajas, C. Wandrey and D. Hunkeler, U.S. Pat. 6,667,374 B1 (2003). • The chosen healthy-friendly oils are suitable to produce copolymers with high molecular weight and different charge densities, in stable emulsions, without affecting the final target viscosity by the use of a different organic phase and surfactants combination. • These processes have good possibilities to work successfully when applied with new co- and ter-polymers developed to treat wastewaters. INVERSE-EMULSION POLYMERIZATION CONCLUSIONS 2 nd EuCheMS Congress on Green and Sustainable Chemistry Conditions Monomers concentration 40 wt% Surfactants Sorbitan isostearate PEG-7 Hydrogenated Castor oil HLB 4.75 (Puresyn 4) 5.50 (Carnation) 4.75 (Marcol 82) Initial temperature 25-30 o C Initiator Redox couple: Tert-butyl hydroperoxide/ Meta bisulfite Organic phases • Puresyn 4 • Carnation • Marcol 82 Copolymers • 60%AAm_40%AETAC • 40%AAm_60%AETAC • 20%AAm_80%AETAC Acrylamide (AAm) 2-(Dimethylamino)ethyl acrylate (AETAC) EVALUATION OF PERFORMANCE USING SLUDGE Reference MEASUREMENT OF VISCOSITY The polymer viscosity was measured using a 0.5 wt% of active polymer solution with a model LVDVII þ viscometer (Brookfield, Stoughton, MA, USA) at 30 rpm and 24-25 o C temperature. ƞ (mPa.s) Puresyn4_60%AAm_40%AETAC 1093 Carnation_60%AAm_40%AETAC 1130 Marcol82_60%AAm_40%AETAC 1003 ƞ (mPa.s) Puresyn4_40%AAm_60%AETAC 1200 Carnation_40%AAm_60%AETAC 1210 Marcol82_40%AAm_60%AETAC 1313 ƞ (mPa.s) Puresyn4_20%AAm_80%AETAC 1333 Carnation_20%AAm_80%AETAC 1103 Marcol82_20%AAm_80%AETAC 1030

DEVELOPMENT OF FLOCCULANTS USING HEALTHY …DEVELOPMENT OF FLOCCULANTS USING HEALTHY-FRIENDLY PROCESSES A. Lourenço 1,2, J. Arnold 2 and M. G. Rasteiro 1,* 1 Chemical Engineering

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DEVELOPMENT OF FLOCCULANTS USING HEALTHY-FRIENDLY PROCESSES

A. Lourenço 1,2, J. Arnold 2 and M. G. Rasteiro 1,*

1 Chemical Engineering Department, University of Coimbra, Rua Sílvio Lima, 3030-790 Coimbra, Portugal.2 Aqua+Tech Specialities SA, 1237 Avully, Geneva, Switzerland.

[email protected], [email protected]*

The main objective of this work is the development of new flocculants medium using healthy-friendly ingredients in their synthesis. A new polymerization

medium has been tested with a well-known copolymer for water treatment formulations, consisting of cationic quaternary ammonium and acrylamide

monomers. As these polymers are produced in inverse-emulsion, alternative continuous phases can be employed including purified mixtures of liquid saturated

hydrocarbons, with higher boiling point. Those are of high purity due to their manufacturing process being free of the toxic polycyclic aromatics and heavy metals.

Polyacrylamide-co-dimethylaminoethyl acrylate (AAm_AETAC) was synthesized with three different oils and three different polymer compositions, in order to

evaluate if it is possible to produce copolymers with controlled properties and different charge densities using the previous mentioned healthy-friendly oils. The

results showed that these oils are suitable to produce copolymers with high molecular weight and having different charge densities, keeping the emulsion

stability unchanged. In addition, a further step could be achieved by partially replacing the ethoxylated surfactant.

ACKNOWLEDGEMENTSThe authors would like to thank for financial support from Marie Curie Actions – European Industrial Doctorate (EID), through Grant agreement FP7-PEOPLE-2013-ITN-604825, and from Portuguese Foundation for Science and Technology (Pest/C/EQB/UI0102/2013). Also, to Dr. David Hunkeler and Aqua+Tech Specialities SA (Switzerland).REFERENCESM. G. Rasteiro, F. A. P. Garcia, P. J. Ferreira, E. Antunes, D. Hunkeler and C. Wandrey, J. Appl. Polym. Sci. 2010, 116, p. 3603–3612.J. Hernandez Barajas, C. Wandrey and D. Hunkeler, U.S. Pat. 6,667,374 B1 (2003).

• The chosen healthy-friendly oils are suitable to produce copolymers with high molecular weight and different charge densities, in stable emulsions,without affecting the final target viscosity by the use of a different organic phase and surfactants combination.

• These processes have good possibilities to work successfully when applied with new co- and ter-polymers developed to treat wastewaters.

INVERSE-EMULSION POLYMERIZATION

CONCLUSIONS

2nd EuCheMS Congress on Green and Sustainable Chemistry

Conditions

Monomers concentration 40 wt%

Surfactants Sorbitan isostearate

PEG-7 Hydrogenated Castor oil

HLB

4.75 (Puresyn 4)

5.50 (Carnation)

4.75 (Marcol 82)

Initial temperature 25-30 oC

Initiator Redox couple: Tert-butyl hydroperoxide/ Meta bisulfite

Organic phases

• Puresyn 4

• Carnation

• Marcol 82

Copolymers

• 60%AAm_40%AETAC

• 40%AAm_60%AETAC

• 20%AAm_80%AETAC

Acrylamide (AAm)

2-(Dimethylamino)ethyl acrylate(AETAC)

EVALUATION OF PERFORMANCE USING SLUDGE

Reference

MEASUREMENT OF VISCOSITY

The polymer viscosity wasmeasured using a 0.5 wt% ofactive polymer solution witha model LVDVII þ viscometer(Brookfield, Stoughton, MA,USA) at 30 rpm and 24-25 oCtemperature.

ƞ (mPa.s)

Puresyn4_60%AAm_40%AETAC 1093

Carnation_60%AAm_40%AETAC 1130

Marcol82_60%AAm_40%AETAC 1003

ƞ (mPa.s)

Puresyn4_40%AAm_60%AETAC 1200

Carnation_40%AAm_60%AETAC 1210

Marcol82_40%AAm_60%AETAC 1313

ƞ (mPa.s)

Puresyn4_20%AAm_80%AETAC 1333

Carnation_20%AAm_80%AETAC 1103

Marcol82_20%AAm_80%AETAC 1030