catalytic wet peroxide oxidation (cwpo): potential ... · pdf filecatalytic wet peroxide...

Catalytic Wet Peroxide Oxidation (CWPO): Potential applications and challenges

Juan J. Rodriguez

[email protected]

CWPO

Homogeneous Fenton Process

Fe2+ + H2O2 Fe3+ + OH- + OH●

High oxidation capacity

THE FENTON PROCESS

acidic pH

CODinitial + H2O2 Fe2+

PARTIALLY OXIDIZED

COMPOUNDS + H2O2

Fe2+ CO2 + H2O INORGANIC SALTS REFRACTORY COMPOUNDS

influent

sludge

adjust pH

Fe2+

H2O2

re-adjust pH

Fe3+

CWPO

SOME WORKS IN CATALYTIC WET PEROXIDE OXIDATION

AC-based catalysts

Other materials

• J.A. Zazo, J.A. Casas, A.F. Mohedano, J.J. Rodriguez. Catalytic wet peroxide oxidation of phenol with a Fe/active carbon catalyst. Appl. Catal. B., 65 (2006) 261-268.

• C.M. Domínguez, P. Ocón, A. Quintanilla, J.A. Casas, J.J. Rodriguez. Highly efficient application of activated carbon as catalyst for wet peroxide oxidation. Appl. Catal. B., 65 (2006) 261-268.

• R.S. Ribeiro, A.M.T. Silva, J.L. Figueiredo, J.L. Faria, H.T. Gomes. Removal of 2-nitrophenol by catalytic wet peroxide oxidation using carbon materials with different morphological and chemical properties. Appl. Catal. B., 140-141 (2013) 356-362.

• C.B. Molina, A.H. Pizarro, V.M. Monsalvo, A.M. Polo, A.F. Mohedano, J.J. Rodriguez. Integrated CWPO and biological treatment for the removal of 4-chlorophenol from water. Sep. Sci. Technol., 45 (2010) 1595-1602.

• M. Munoz, Z.M. de Pedro, N. Menendez, J.A. Casas, J.J. Rodriguez. A ferromagnetic g-alumina-supported iron catalyst for CWPO. Application to chlorophenols. Appl. Catal. B., 136-137 (2013) 218-224.

• R.S. Ribeiro, Z. Frontistis, D. Mantzavinos, D. Venieri, M. Antonopoulou, I. Konstantinou, A.M.T. Silva, J.L. Faria, H.T. Gomes. Magnetic carbon xerogels for the catalytic wet peroxide oxidation of sulfamethoxazole in environmentally relevant water matrices. Appl. Catal. B., 199 (2016) 170-186.

CWPO

CATALYTIC WET PEROXIDE OXIDATION

CWPO

HIGHTLIGHT RESULTS IN CWPO OF PHENOL

CATALYST Fe

(%, wt.)

WCAT

(g/L)

Phenol

(mM)

H2O2/Phenol

(stoich)

T

(ºC) pH0

Time

(min)

XPh

(%)

XTOC

(%)

FeLeach

(mg/L) Ref. Author

Fe2O3/CeO2 5 1 53 1.32 70 --- 240 78 57 <0.25 Massa et. al., 2008

Fe-ZSM-5 2 0.35 69 1.5 70 3.5 180 81 17 1 Fajerwerg et. al., 1996

Fe-Al-PILC 3.01 5 0.5 1.1 25 3.7 240 100 65 0.2 Guelou et. al., 2003

Fe-Al-PILC 7.2 0.5 1.06 1 25 3.5 240 100 60 2.0 Molina et al. 2006

Fe/Al2O3 7.67 1 1 1.1 --- --- 120 100 60 6.5 Al Hayek et. al., 1984

Fe/SiO2 1.5 0.35 69 1.5 70 3.5 180 65 19 5 Fajerwerg et. al., 1996

Fe-Resin 27.5 5 10.6 0.67 80 3 120 100 76 --- Liou et. al., 2005

Fe/AC 4 0.5 1.06 1 50 3 120 100 78 1.1 Zazo et. al., 2006

CWPO

How is it expected to work?

OH

H2O2

OH·

H2O2

O2 + H2O Fe2O3

Active Carbon

Fe/AC CATALYST

AC Fe/AC

SBET (m2/g) 974 781

Pore volume (cm3/g) 0.75 0.67

Micropore 0.34 0.27

Mesopore 0.19 0.16

Macropore 0.22 0.24

Fe content (% w/w ) - 4

CESEP’09 Carbon for Energy Storage and Environment Protection 2009

CWPO

CATALYTIC WET PEROXIDE OXIDATION

0.00 0.05 0.10 0.15 0.20 0.25 0.300.0

0.2

0.4

0.6

0.8

1.0

1.2

kd (

h-1)

io (A/g)

G-F CB-C

G-S-HCl

CB-V

AC-P-HNO3

AC-P

G-S

AC-M- HCl

AC-M

Relationship between the current exchange (io) and the H2O2 decomposition (kd) for the carbon materials tested

Carbon materials as catalysts: activity prediction by redox properties

FENTON OXIDATION OF PHENOL: REACTIO PATHWAY

J.A. Zazo, J.A. Casas, A.F. Mohedano, M.A. Gilarranz, J.J. Rodriguez. Environ. Sci. Technol. 39 (2005) 9295-9302


CWPO

Compound EC50

(mg/L)

TU (100 mg/L)

Aromatics

Phenol 16 6.3

Catechol 8 12.5

Resorcine 215 0.5

Hydroquinone 0.041 2400

p-Benzoquinone 0.1 1000

Organic

Acids

Muconic 250 0.4

Maleic 250 0.4

Fumaric 250 0.4

Malonic 450 0.2

Acetic 130 0.8

Formic 162 0.6

Oxalic >450 <0.2

CWPO OF PHENOL: ECOTOXICITY OF OXIDATION BYPRODUCTS

CWPO

Fe/AC CATALYST

0 50 100 150 200 250

0

1

2

3

4

5

aro

ma

tic

in

term

ed

iate

s (

mg

/L)

catechol

hydroquinone

p-benzoquinone

0.0

0.2

0.4

0.6

0.8

1.0

time (min)

XH

2O

2

H2O

2

0 50 100 150 200 250

0

2

4

6

8

10

time (min)

maleic fumaric

oxalic acetic

formic

sh

ort

-org

an

ic a

cid

s (

mg

/L)

Operating cond: T: 50ºC ; pH0: 3; 100 mg/L phenol, 500 mg/L H2O2, 500 mg/L Fe/AC

Batch experiments

J. A. Zazo, J. A. Casas, A.F. Mohedano, J. J. Rodriguez. Appl. Catal. B Environ. 65 (2006) 261-268

CWPO

HIGHTLIGHT RESULTS IN CWPO OF PHENOL

CATALYST Fe

(%, wt.)

WCAT

(g/L)

Phenol

(mM)

H2O2/Phenol

(stoich)

T

(ºC) pH0

Time

(min)

XPh

(%)

XTOC

(%)

FeLeach

(mg/L) Ref. Author

Fe2O3/CeO2 5 1 53 1.32 70 --- 240 78 57 <0.25 Massa et. al., 2008

Fe-ZSM-5 2 0.35 69 1.5 70 3.5 180 81 17 1 Fajerwerg et. al., 1996

Fe-Al-PILC 3.01 5 0.5 1.1 25 3.7 240 100 65 0.2 Guelou et. al., 2003

Fe-Al-PILC 7.2 0.5 1.06 1 25 3.5 240 100 60 2.0 Molina et al. 2006

Fe/Al2O3 7.67 1 1 1.1 --- --- 120 100 60 6.5 Al Hayek et. al., 1984

Fe/SiO2 1.5 0.35 69 1.5 70 3.5 180 65 19 5 Fajerwerg et. al., 1996

Fe-Resin 27.5 5 10.6 0.67 80 3 120 100 76 --- Liou et. al., 2005

Fe/AC 4 0.5 1.06 1 50 3 120 100 78 1.1 Zazo et. al., 2006

CWPO

Continuous experiments

stirred tank reactor

0 20 40 60 80 100 120 140 160

0.0

0.2

0.4

0.6

0.8

tos (h)

H2O

2 /

H2O

2

init

ial

H2O

2 / H

2O

2 initial

0

1

2

3

4

Fe

leach

ed (

mg

/L)

Fe leached (mg/L)

0.0

0.2

0.4

0.6

0.8

1.0

ph

en

ol / p

hen

ol

init

ial

phenol / phenol initial

Adsorption

Reaction

0.0

0.2

0.4

0.6

0.8

1.0

TO

C / T

OC

init

ial

TOC / TOCinitial

Working conditions

Q: 5 mL/min

Phenol: 100 mg/L

H2O2: 500 mg/L

pH: 3

Temperature: 50 ºC

Vreaction: 0.92 L

HRT: 184 min ; : 167 gcat.h/gPh

Wcatalyst: 5.4 g/L


CWPO

O

C C

HO OH

O

Fe2O3

0 5 10 15 20

0

2

4

6

8

Fe

leached (

mg/L

)

oxalic acid (mg/L)


Fe leached (mg/L): 0.35 · oxalic acid (mg/L)

r: 0.98

J. J. Rodríguez CWPO

Catalyst (Fe/C)BULK (Fe/C)XPS

Fe/C1-N 0.013 0.005

Fe/C2-N 0.012 0.026

Fe/C3-N 0.013 0.045

Fe/C1-P 0.009 0.013

Fe/C2-P 0.010 0.013

Fe/C3-P 0.009 0.012

Fe/C atomic ratios of catalysts

homogeneous

egg-shell

egg-yolk

A. Rey, M. Faraldos, J. A. Casas, J. A. Zazo, A. Bahamonde, J. J. Rodríguez. Appl. Catal. B Environ. 86 (2009) 69

Effect of Iron Precursor & AC support

Incipient wetness impregnation Fe: 4%

Iron nitrate (N) aqueous solution

Iron pentacarbonyl (P) organic medium

CWPO

% Fe leached from Fe/AC and the new catalyst in presence of oxalic acid (100 mg/L)

Comparision of the catalytic activity of Fe/AC and the new catalyst

0 50 100 150 200 250

0.0

0.2

0.4

0.6

0.8

1.0

time (h)

Fe/AC (4% Fe) (50ºC)

New catalyst (50ºC)



Xphenol

0 5 10 15 20 25

0

20

40

60

80

100

Fe/CA (4% Fe)

New catalyst

% F

e leached

time (h)

CWPO

Long-term stability of the Fe (4%)/γ-Al2O3 catalyst in CWPO of cosmetic wastewater T = 85 ºC;

space-time: 9.8 kg cat.h/kg COD

0 20 40 60 80 100

20

40

60

80

100

COD

TOC

Co

nvers

ion

(%

)

Time on stream (h)

Cosmetic wastewater with Fe/γ-Al2O3

Ingeniería Química

Universidad Autónoma de Madrid


Applications of Activated Carbons in Catalytic

Processes for the abatement of water

pollutants

LOGO

CWPO

Economic Analysis (€ /m3)

Fenton (homogeneous)

CWPO with Fe/γ-Al2O3

Investment 1.35 1.40

Operation & Maintenance

H2O2 2.20 1.80

Catalyst 0.10 0.06

Other 0.20 0.20

Electricity (1.9 kW-h/m3) 0.17 0.17

Heat (32 MJ/m3) 0.25

Sludge treat & disposal (30 €/t)

0.30

Cosmetic wastewaters (100 m3/d) 4.32 3.88

COD0: 3000 mg/L 200 mg/L Fe2+ 5g/L Fe/AC, 100 h

CODf: 1200 mg/L 3800 mg/L H2O2 2900 mg/L H2O2

CWPO

FexOy/g-Al2O3 catalysts for CWPO

Magnetic catalyst

0 30 60 90 120 150 180 210 2400

15

30

45

60

75

TO

C (

mg·L

-1)

time (min)

Fenton process Fe2O

3/g-Al

2O

3 Fe

3O

4/g-Al

2O

3

4 % Fe

Incipient wetness impregnation with ferric nitrate

Calcination at 300 ºC

Magnetic catalyst: Reduction at 350 ºC


CWPO

CWPO of CPs with FexOy/g-Al2O3

Evolution of 4-CP, 2,4-DCP and 2,4,6-TCP upon homogeneous Fenton oxidation ([Fe3+]0 = 10 mg L-1) and CWPO with FexOy/g-Al2O3 (1 g L-1); ([CP]0 = 100 mg L-1; [H2O2]0 at stoichiometric dose; pH0 = 3; T = 50 ºC).

0 30 60 90 120 150 180 210 2400

20

40

60

80

100

0

20

40

60

80

100

0

20

40

60

80

100

time (min)

conc

entr

atio

n (m

g·L-1

)

Fe2O

3/g-Al

2O

3

Fe3O

4/g-Al

2O

3

Homogeneous Fenton

2,4,6-TCP

2,4-DCP

4-CP

M. Munoz, Z.M. de Pedro, J.A. Casas, J.J. Rodriguez. Chem. Eng. J. 228(2013) 646-654

Fenton provides more rapid conversion of the starting CP


CWPO


Evolution of TOC and H2O2 upon homogeneous Fenton oxidation ([Fe3+]

0 = 10 mg L-1) and CWPO with FexOy/γ-Al2O3 (1 g L-1); ([CP]0 = 100 mg L-1; [H2O2]0 at stoichiometric dose; pH0 = 3; T = 50 ºC).

10

20

30

40

50

60

20

40

60

80

100

4-CP

10

20

30

40

50

TO

C (

mg

·L-1)

20

40

60

80

100

Fe2O

3/g-Al

2O

3

Fe3O

4/g-Al

2O

3

Homogeneous Fenton

2,4-DCP

XH

2 O2 (%

)

0 30 60 90 120 150 180 210 2400

10

20

30

40

time (min)

30 60 90 120 150 180 210 2400

20

40

60

80

100

2,4,6-TCP

CWPO more efficient than Fenton in terms of mineralization


CWPO


Evolution of TOC vs. H2O2 conversion upon 4-CP breakdown by homogeneous Fenton oxidation ([Fe3+]0 = 10 mg L-1) and CWPO with FexOy/g-Al2O3 (1 g L-1); ([4-CP]0 = 100 mg L-1; [H2O2]0 = 350 mg L-1; pH0 = 3).

0 20 40 60 80 1000

20

40

60

80

100

20

40

60

80

100

XH

2O

2

(%)

90 ºC

50 ºC

Fe2O

3/g-Al

2O

3

Fe3O

4/g-Al

2O

3

Homogeneous Fenton

XT

OC (

%)

CWPO allows more efficient consumption of H2O2

H2O2 + Fe2+ + H+→ HO. +Fe3+ + H2O

H2O2 + Fe3+ +H+→ HOO. +Fe2+ + H+

HO. + HOO. → H2O + O2

HO. + H2O2 → H2O + HOO.

HOO. + Fe3+→ Fe2+ + O2 + H+

HOO. + Fe2+→ Fe3+ + HOO-


CWPO


Remaining by-products (4h) from chlorophenols oxidation by homogeneous Fenton ([Fe3+]0 = 10 mg L-1) and CWPO with FexOy/g-Al2O3 (1 g L-1) at 50 and 90 ºC ([CP]0 = 100 mg L-1; [H2O2]0 at stoichiometric dose; pH0 = 3).

10

20

30

40

90

100

% o

f initia

l C

% o

f in

itia

l C

Hom

ogen

eous

Fen

ton

Fe 3O 4

/g-Al 2O 3

Fe 2O 3

/g-Al 2O 3

Hom

ogen

eous

Fen

ton

Fe 3O 4

/g-Al 2O 3

Fe 2O 3

/g-Al 2O 3

10

20

30

40

90

100

2,4,6-TCP

2,4-DCP

4-CP

50 ºC 90 ºC

Condensatioin by-products

Organic acids

0

10

20

30

40

90

100

10

20

30

40

90

100

10

20

30

40

90

100

0

10

20

30

40

90

100

CWPO

Chlorinated byproducts from Fenton oxidation of MCPs

M. Munoz, Z.M. de Pedro, J.A. Casas, J.J. Rodriguez. J. Haz. Mat. 190 (2011) 993-1000

CWPO

Chlorinated byproducts from Fenton-like oxidation of PCPs

M. Munoz, Z.M. de Pedro, G. Pliego, J.A. Casas, J.J. Rodriguez Ind. Eng. Chem. Res. 51 (2012) 13092-13099

a Chlorinated byproducts from Fenton-like oxidation of PCPs

M. Munoz, Z.M. de Pedro, G. Pliego, J.A. Casas, J.J. Rodriguez. Ind. Eng. Chem. Res. 51 (2012) 13092-13099


CWPO


Evolution of 4-CP, 2,4-DCP and 2,4,6-TCP (in equivalent Cl; solid symbols) and chloride ion (open symbols) concentration upon CWPO with FexOy/g-Al2O3 catalysts. ([CP]0 = 100 mg L-1; [FexOy/g-Al2O3]0 = 1 g L-1; [H2O2]0 = stoichiometric dose; pH0 = 3; T = 50 ºC).

0 30 60 90 120 150 180 210 2400

300

600

900

1200

1500

0

300

600

900

1200

1500

time (min)

Fe3O

4/g-Al

2O

3

4-CP

2,4-DCP

2,4,6-TCP

co

ncen

tra

tio

n (M

)

Fe2O

3/g-Al

2O

3

Complete dechlorination


CWPO


TOC and H2O2 conversion (4 h) upon CWPO of 2,4,6-TCP with the FexOy/g-Al2O3 catalysts in successive applications ([FexOy/g-Al2O] 0 = 1 g L-1). ([2,4,6-TCP]0 = 100 mg L-1; [H2O2]0 = 190 mg L-1; pH0 = 3; T = 90 ºC).

0

20

40

60

80

100

H2O

2

1st run 2nd run 3rd run

X (%

)

Fe3O

4/g-Al

2O

3Fe

2O

3/g-Al

2O

3

TOC H2O

2TOC

0

20

40

60

80

100

X (%

)


CWPO

Magnetic Fe/g-Al2O3 catalyst

Magnetization curves at room temperature of the FexOy/g-Al2O3 catalyst before and after CWPO oxidation of 4-CP at different temperatures.

-10000 -5000 0 5000 10000

-2

-1

0

1

2

M (

em

u·g

-1)

H (Oe)

Fresh catalyst

Used catalyst at 50 ºC



CWPO

CWPO OF REPRESENTATIVE DRUGS OVER Fe3O4/g-Al2O3

Operating conditions [pharmaceuticals]0 = 25 mg L-1

[H2O2]0 = stoichiometric amount

[Fe3O4/g-Al2O3]0 = 2 g L-1

50 - 75 ºC pH0 = 3

Atenolol

ATL

Trimethoprim

TMP

Ranitidine

RTD

Munoz et al., J. Hazard. Mater., 331 (2017) 45-54.

Antibiotics

b and calcium channel blockers

Antiulcer

CWPO


First order

kinetics

49.5

(kJ mol-1)

Activation energy values

67.0

45.6 65.7 58.3

82.9

CWPO


SMX DTZ TMP ATL RTD MNZ

0

20

40

60

80

100

0

20

40

60

80

100

XT

OC (%

)

H2O

2 c

on

su

mp

tio

n e

ffic

ien

cy (

%)

TMP

SMX

DTZ

ATL

RTD MNZ

CWPO

STABILITY TESTS

0 15 30 45 60

5

10

15

20

25

MNZ

SMX

ATL

TMP

DTZ

RTD

3rd run2

nd run

concentr

ation (

mg L

-1) 1

st run

15 30 45 60

time (min)

15 30 45 60

Operating conditions [pharmaceuticals]0 = 25 mg L-1

[H2O2]0 = 730 mg L-1

[Fe3O4/g-Al2O3]0 = 2 g L-1

75 ºC pH0 = 3

Iron leaching < 1.5% wt.

Absence of carbon deposits

Surface area unchanged

CWPO

OPERATION AT REPRESENTATIVE CONCENTRATIONS (g L-1)

Operating conditions [pharmaceuticals]0 = 10 g L-1

[H2O2]0 = 100 mg L-1

[Fe3O4/g-Al2O3]0 = 2 g L-1

75 ºC pH0 = 3

0 5 10 15 20 25 30

0

2

4

6

8

10 MNZ

SMX

ATL

TMP

DTZ

RTD

co

nce

ntr

atio

n (

g L

-1)

time (min)

Complete removal of pharmaceuticals

(30 min)

Hospital wastewater WWTP effluent

2.6

4.5

11.6

0.9

1.6

2.4

1.2

7.6

0.3

0.1

3.1

0.5

SMX

ATL

MNZ

DTZ

TMP

RTD

Concentration (g L-1)

CWPO

CWPO OF SULFOMETHOXAZOLE WITH NATURAL MAGNETITE

Operating conditions [SMX]0 = 5 mg L-1

[H2O2]0 = 25 mg L-1

[Fe3O4]0 = 1 g L-1

25 ºC pH0 = 5

Iron leaching < 0.5 mg L-1

Absence of carbon deposits (<0.1% wt.)

Surface area and magnetic properties unchanged

0 60 120 180 240

0

20

40

60

80

100

SM

X c

on

ve

rsio

n (

%)

time (min)

Catalyst reuse (3 consecutive runs)

Fe3O4 1

st run

2nd

run

3rd run

0 50 100 150 200 250 300 350 4000

2

4

6

8

10

12

C s

hort

chain

acid

s (

mg

·L-1)

t (min)

acetic

formic

malonic

maleic

fumaric

oxalic

0

2

4

6

8

C a

rom

atics (

mg

·L-1)

Hidroquinone

Resorcinol

Cathecol

Benzoquinone

0

20

40

60

80

100

C H

2O

2 (mg

·L-1)

C P

henol/T

OC(m

g·L

-1)

Phenol

TOC

0

100

200

300

400

500

H2O

2

Feleach< 1 mg·L-1

XTOC>97%

Conditions

25 ºC pH0 = 3

I=550 W·m-2

[Phenol] 0 = 100 mg·L-1

[H2O2]0 = 500 mg·L-1

[ILM-Fe(x)] = 450 mg·L-1

CWPO/solar with ilmenite

P. García-Muñoz, G. Pliego, J.A. Zazo, A. Bahamonde, J.A. Casas. Journal of Environmental Chemical Engineering 4 (2016) 542-548.

Thank you!

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