Oxidation of Pharmaceuticals and Personal-Care ... - Dynaflow, Inc.

Oxidation of Pharmaceuticals and Personal-Care Products in Water using Hydrodynamic Cavitation 245th American Chemical Society Meeting April 10, 2013

Authors

Greg Loraine and Georges L. Chahine Dynaflow, Inc. 10621-J Iron Bridge Road Jessup, MD 20794 U.S.A.

www.dynaflow-inc.com

ACS 245th

4-10-13

Outline  Cavitation and Formation of Free Radicals  Acoustic (Ultrasonic) Cavitation vs. Hydrodynamic Cavitation  Hydrodynamic Cavitating Jets  Chloramphenicol  Pharmaceuticals and Personal-Care-Products in Wastewater  Conclusions


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6000 V spark. Collapse is analogous to cavitation

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Cavitation  Bubble nuclei in water expand & collapse when the local pressure changes very quickly.  Collapsing bubbles produce tremendous pressures & temperatures in localized area (~5,200 K, ~200 Atm).  Water vapor dissociates into OH• and H• H2O → OH• + H•  Volatile compounds can also dissociate into radicals CCl4 → Cl• + Cl3C• www.dynaflow-inc.com

Radius of Bubble

Pressure

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Reaction Location Collapsing Bubble

Parent Concentration

 Reactions occur inside collapsing bubble or at interface  OH• and H• concentrations highest in center, decrease toward bubble wall  Hydrophobic compounds partition to air-water interface  Local depletion of starting compound and build up of products  Volatile compounds enter the expanding bubble and decompose during collapse

OH• H• Products


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Products 4-10-13

Hydrodynamic & Ultrasonic Cavitation  Ultrasonic (US) cavitation produced by mechanical vibration in a liquid localized at the face of the probe.  US- high intensity, localized cavitation, energy intensive, scaling up difficult  Hydrodynamic Cavitation (HD) is produced by motion of fluid. All liquid is forced through cavitation region  Large pressure fluctuations in shear layer of the liquid cause cavitation.  HD – wider area of cavitation, 1/10 – 1/100 energy required, easy to scale www.dynaflow-inc.com

ACS 245th

US

HD

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DYNAJETS® Cavitating Jets  Specially designed nozzles intensify cavitation and generate cavitation at lower pump pressures  This is achieved through:  Bluff body  Swirling the flow  Passive acoustic excitation  Enhance vorticity and reduce pressure in the vortices

DYNASwirl®

Area of Cavitation

Centerbody CAVIJET® www.dynaflow-inc.com

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Hydrodynamic Cavitation for Oxidation  Hydrodynamic cavitation can be 10 – 100 times more energy efficient than acoustic cavitation  No addition of oxidizer  Optical opacity or particulates are no problem  Other than nozzle no special equipment required  Specially designed submerged nozzles (DYNAJETS®)  Cavitation at lower pressures  Lower pressures lower electrical requirements  Hydraulic Energy = Flow Rate x Pressure Change x Time  Cavitation in wider area  Easier to scale up than US www.dynaflow-inc.com

ACS 245th

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C/C0 P-Nitrophe nol

1

Note Much More Rapid Concentration Drop with the DYNAJETS ® .

0.8 ULTRASONIC

0.6 DYNAJETS®

0.4 0.2

Oxidation Efficency, mg/MJ

Energy: Acoustic & Hydrodynamic 10 Note High Oxidation Efficency and Short Oxidation Time for DYNAJETS ® . 1

DYNAJETS®

0.1 ULTRASONIC 0.01 0

0 0

10

20 Time, Hours

30

40

5

10

15

20

25

30

35

Time, Hours

25 ppm p-Nitrophenol

 Hydrodynamic cavitation can be 10 – 100 times more energy efficient than acoustic cavitation* *K.Kalumuck, G. Chahine, J. Fluids Eng., 122,(2000) 465. S. Majumdar, P. S. Kumar, A. Pandit, Ultra. Sonochem., 5 (1998) 113. K. Jyoti, A. Pandit, Water Res., 38 (2004), 2249.


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Previous Work using DYNAJETS®  Oxidation  Pharmaceuticals and Personal Care Products  Chlorinated solvents  Toluene, Acetone  Pesticides: Malathion, Carbaryl, 2,4-D  Disinfection  Water  Wastewater  Storm water  Recovery of Cellular Matter – Algae  Pretreatment of lignocellulose biomass  Biodiesel production www.dynaflow-inc.com

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Selectivity of HD Cavitation Oxidation  Volatile (high vapor pressure) can be oxidized easily  Hydrophobic compounds (high octanol-water partition coefficient log KOW) oxidize faster than hydrophilic compounds  pH can be used to adjust degree of ionization of weak acids and bases  Reaction intermediates are formed in regions of high radical concentrations, lower by-product concentrations  Operating parameters (pump pressure, jet velocity, etc.), and nozzle design can be varied to improve oxidation performance


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Chloroamphenicol  2,2-dichloro-N-[1,3-dihydroxy-1-(4-nitrophenyl) propan-2-yl acetamide  Broad spectrum antibiotic  Log KOW = 1.14, pKa = 9.61  Experimental  Oxidized using two types of nozzles  Pressure drops across nozzle 30 – 90 psi (2 – 6.2 bar)  [CA]0 = 30 mg/L in DI water (10 L)  Analytical  Extracted using SDB solid phase extraction disks  GC/MS analysis  LOD 2.4 mg/L & 95% recovery www.dynaflow-inc.com

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Effects of Operating Pressure - DYNASWIRL®  Operating pressure had a large effect on the removal rate,  Nozzle design and geometry also affect performance. DYNASWIRL

30

30 psi 90 psi

25

Chloramphenicol mg/L

60 psi

20

15

10

5 0

20

40

60

80

100

120

140

Oxidation Time, mins.


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Effects of Operating Pressure – Centerbody CAVIJET®  Operating pressure again affected the removal rate,  91% removal centerbody-CAVIJET 30

Chloramphenicol, mg/L

25 65 psi 45 psi

20

15 10 5 0 0

20

40

60

80

100

120

140

Oxidation Time, mins. www.dynaflow-inc.com

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Chloramphenicol Removal per kiloJoule 1.2

Chloramphenicol [C]/[C]0

CAVIJET 65 PSI CAVIJET 45 PSI

1

DYNASWIRL 30 PSI DYNASWIRL 60 PSI

0.8

DYNASWIRL 90 PSI

0.6 0.4 0.2

0 0

100

200

300

400

500

600

kJ


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Chloramphenicol: Product Formation and Mass Balance 120

120 Mass Balance

100

80

80 Chloramphenicol

60

60 4-Dichloromethyl Oxazoline

40

40 Nitrobenzaldehyde

20

Mass Balance

Concentration, mM

100

20

0

0 0

50

100

150

Time (mins.) www.dynaflow-inc.com

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Proposed Mechanism of Chloramphenicol Oxidation Cl

Cl N

NO2

C Cl

C

NO2

+ •OH

•

C O

Cl

NO2

+

•

N

Cl

N

C

C

Cl

O

OH

H2O +

C C

4-Nitrobenzaldehyde

C

Cl

C

OH

OH

O

N

Cl

N

C

O

Cl

C Cl

C

OH

O

2-dichloromethyl oxazoline www.dynaflow-inc.com

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Selective Oxidation of Mixtures: log KOW  Seven

PPCP spiked into filtered wastewater TP effluent  Oxidized using a DYNASWIRL® nozzle  Range of Log KOW Compound

Primary Use

Spiked concentration

MDL g/L*

g/L

Concentration Range in Wastewater Effluent ug/L

Log KOW

14.4

1.44

1.9 – 6.9

2.48

Triclosan

Pharmaceutic al Anti-microbial

3.46

0.346

0.6 – 4.7

4.79

Chloroxylenol

Anti-microbial

0.146

0.015

0.03 – 0.05

5.9

Galaxolide

Fragrance

6.14

0.614

0.7 – 2.6

5.9

Musk Ketone

Fragrance

0.33

0.034

0.06 – 0.11

4.31

Oxybenzone

Sun-screen

0.6

0.06

0.18 – 0.35

3.79

Tris (2chloroethyl) Phosphate

Flame retardant

1.79

0.35

0.35 – 0.39

1.44

Ibuprofen


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Oxidation of Mixture of PPCP in Wastewater 1.100

Log KOW 1.44 2.48

1.000

4.31

C/C0

0.900

3.79 4.76

0.800

Chloroxylenol Tris(2-chloroethyl)Phosphate

5.9

Galaxolide Musk Ketone

0.700

5.9

Oxybenzone Triclosan Ibuprofen

0.600 0

5

10

15

20

25

30

Time (mins.)

DYNASWIRL® nozzle at 60 psi www.dynaflow-inc.com

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Log KOW and Reaction Extent 0.35 y = 0.05x - 0.0385 R2 = 0.7906

0.3

(1-C/C0)

0.25 0.2 0.15 0.1 0.05 0 0

1

2

3

4

5

6

7

log Kow

In a mixture more hydrophobic compounds react faster www.dynaflow-inc.com

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Conclusions  Cavitation initiated reactions are similar regardless of how the cavitation is initiated  Hydrodynamic cavitation can be more energy efficient and easier to scale up than ultrasonic devices  Selective removal of volatile and hydrophobic compounds can be accomplished  Oxidation rates have non-linear dependence on pump pressure  Nozzle geometry can affect oxidation rates www.dynaflow-inc.com

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Acknowledgements & Contact Information  US Environmental Protection Agency  NASA  Office Naval Research  NOAA  NIEHS

DYNAFLOW, INC. www.dynaflow-inc.com 10621-J Iron Bridge Road, Jessup, MD 20794. USA Dr. Greg Loraine Sr. Research Scientist (301) 604-3688

[email protected] Dr. Georges L. Chahine President (301) 604-3688 [email protected]

Business POC: Dr. Jin-Keun Choi Principal Research Scientist (301) 604-3688 [email protected] www.dynaflow-inc.com

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