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WASTEWATER

TREATMENT BY
HIGH EFFICIENCY
HETEROGENEOUS
PHOTO-FENTON
PROCESS

Massimo Ricciardi
Unione Europea UNIVERSITÀ DEGLI
STUDI DI SALERNO

Fondo sociale europeo


Programma Operativo Nazionale 2000/2006
“Ricerca Scientifica, Sviluppo Tecnologico, Alta Formazione”
Regioni dell’Obiettivo 1 – Misura III.4
“Formazione superiore ed universitaria”
Department of Chemical and Food Engineering
Ph.D. Course in Chemical Engineering
(III Cycle-New Series)

WASTEWATER TREATMENT BY HIGH


EFFICIENCY HETEROGENEOUS PHOTO-
FENTON PROCESS

Supervisor Ph.D. student


Prof. Paolo Ciambelli Ing. Massimo Ricciardi

Scientific Referees
Prof. Diana Sannino
Prof. Lyubov A. Isupova

Ph.D. Course Coordinator


Prof. Paolo Ciambelli
To my family
Acknowledgments

In onore alla verità, lo spazio per le gratitudini potrebbe occupare un


capitolo di questa tesi, e più che un'esagerazione è una maniera di esprimere
l’avere avuto la fortuna di lavorare con tanta gente e dalla quale ho ricevuto
sempre aiuto, stima, amicizia e solidarietà, ragioni per le quali sono molto
grato.

In primo luogo voglio ringraziare il Prof. Paolo Ciambelli da cui ho


ricevuto fiducia, conoscenze e tutto il suo aiuto per portare a termine questa
tesi di dottorato.

Un ringraziamento particolare va alla Prof.ssa Diana Sannino, per il suo


appoggio durante tutte le fasi di questo lavoro e per l'aiuto che mi ha offerto
quando ho avuto bisogno di lei; a lei, devo, infatti, il raggiungimento di
questo importante traguardo.

Voglio inoltre ringraziare il Prof. Vincenzo Palma per la sua disponibilità


e per la sua costante presenza durante i tre anni di dottorato.

Un ringraziamento va alla Prof.ssa Lyubov Isupova per la sua proficua


collaborazione e per i suoi preziosi suggerimenti.

Vorrei ringraziare il Sig. Antonio Mormile per la sua puntuale


collaborazione.

Ringrazio la Prof.ssa Paola Russo, il Dr Vincenzo Vaiano, la Dr.ssa


Maria Sarno, la Dott.ssa Ivana Orlando e gli Ingegneri Arianna Ruggiero,
Emma Palo, Giuseppa Matarazzo, Antonietta Maria Manna, Elvirosa
Brancaccio e Caterina Leone che mi hanno fatto capire quanto sia importante
collaborare in un ambiente piacevole e stimolante.

Ma ringrazio soprattutto mia madre, mio padre, mio fratello e Rossella


per avermi sostenuto in ogni occasione.
Publications list

1. P. Ciambelli, D. Sannino, M. Ricciardi, L.A. Isupova;


Monolith perovskites catalyst for photo-Fenton reaction. The
Third European Conference on Oxidation and Reduction
Technologies for ex-Situ Treatment of Water, Air and Soil and
in-Situ Treatment of Soil and Groundwater (ECOR-3)
September 11 - 13, 2006, Göttingen, Germany, p.90-91.
2. P. Ciambelli, D. Sannino, M. Ricciardi, L.A. Isupova;
Monolith supported perovskite catalyst for photo-Fenton
pollutant oxidation. SCI 2006 - XXII congresso nazionale della
Società Chimica Italiana. September 10-15, 2006, Firenze, Italy,
p.276.
Contents

I Introduction ..................................................................................... 1
I.1 Removal of organic compounds............................................... 3
I.1.1 Incineration.......................................................................... 4
I.1.2 Air stripping ......................................................................... 4
I.1.3 Adsorption onto activated carbon ........................................ 5
I.1.4 Wet oxidation ....................................................................... 5
I.1.5 Electrochemical oxidation ................................................... 6
I.1.6 Photochemical processes ..................................................... 7
I.1.7 Biological oxidation ............................................................. 8
I.1.8 Chemical oxidation .............................................................. 8
I.1.8.1 Classical Chemical Treatments...................................... 11
I.1.8.2 Advanced Oxidation Processes (AOPs)......................... 13
I.2 Fenton and photo-Fenton reaction.......................................... 15
I.2.1 Basic Principles ................................................................. 15
I.2.1.1 The Fenton Process........................................................ 15
I.2.1.2 The photo-Fenton process.............................................. 19
I.3 Aim of the work...................................................................... 20
II State of the art ............................................................................... 21
II.1 The homogeneous Fenton reaction......................................... 21
II.2 The heterogeneous Fenton reaction........................................ 22
II.2.1 The heterogeneous Fenton reaction with zeolite ........... 22
II.2.2 The heterogeneous Fenton reaction with perovskite ..... 23
II.3 UV/oxidation processes.......................................................... 23
II.3.1 Photolysis of hydrogen peroxide.................................... 23
II.3.2 The homogeneous photo-Fenton reaction ..................... 25
II.3.3 The heterogeneous photo-Fenton reaction .................... 25
III Experimental methods.............................................................. 29
III.1 Catalyst characterization ........................................................ 29
III.1.1 ICP-MS .......................................................................... 29
III.1.2 Thermal analysis (TG-MS) ............................................ 30
III.1.3 N2 adsorption measurements ......................................... 33
III.1.4 The micro Raman spectroscopy..................................... 33
III.1.5 SEM analysis ................................................................. 34

I
III.1.6 NIR-UV-VIS DRS ........................................................... 35
III.1.7 XRD spectroscopy.......................................................... 35
III.2 Laboratory apparatus for catalytic Fenton oxidation.............. 35
III.3 Laboratory apparatus for catalytic photo-Fenton oxidation.... 37
III.4 Laboratory apparatus for total organic carbon analysis.......... 39
III.5 Analytical method for H2O2 determination............................. 40
IV Experimental results: Fenton oxidation of acetic acid on FeY
zeolite .................................................................................................... 43
IV.1 Samples preparation ............................................................... 43
IV.1.1 The HY based catalyst.................................................... 43
IV.2 Catalysts characterisation ....................................................... 45
IV.2.1 Specific surface area and chemical analysis ................. 45
IV.2.2 X-ray diffraction spectroscopy (XRDS) ......................... 45
IV.3 Catalytic activity tests............................................................. 46
IV.3.1 Homogeneous catalytic Fenton oxidation...................... 46
IV.3.1.1 Acetic acid solution ................................................... 47
IV.3.1.2 Real wastewater......................................................... 47
IV.3.2 Heterogeneous catalytic Fenton oxidation .................... 48
IV.3.2.1 Effect of reaction temperature ................................... 48
IV.3.3 Thermal analysis............................................................ 50
IV.3.4 Leaching test .................................................................. 53
V Experimental results: characterization of the perovskite based
monolith....................................................................................................... 55
V.1 Sample preparation ................................................................. 55
V.2 Thermal analysis..................................................................... 56
V.3 X-ray analysis ......................................................................... 58
V.4 SEM analysis .......................................................................... 59
V.5 Micro Raman spectroscopy .................................................... 60
V.6 Specific surface area ............................................................... 61
V.7 NIR-UV-VIS DRS.................................................................. 61
VI Experimental results: Fenton oxidation of acetic acid on
LaMeO3 perovskite..................................................................................... 65
VI.1 Catalytic activity tests............................................................. 65
VI.1.1 Catalytic decomposition of H2O2 on LaMnO3 and LnFeO3
....................................................................................... 65
VI.1.2 Fenton oxidation of acetic acid on LaMnO3 (3.67%) .... 67
VI.1.3 Fenton oxidation of acetic acid on Pt/LaMnO3 ............. 69
VI.1.4 Fenton oxidation of acetic acid on LaFeO3 (2.24%) ..... 70
VI.1.5 Fenton oxidation of acetic acid on LaCuO3 ................... 72
VI.1.6 Fenton oxidation of acetic acid on LaNiO3.................... 75
VI.1.7 Fenton oxidation of acetic acid on LaCoO3 ................... 77
VI.2 Leaching test........................................................................... 78
VII Experimental results: photooxidation of acetic acid.............. 81
VII.1 Photooxidation test conditions and typical trends .............. 81

II
VII.2 Photolysis reactions............................................................ 84
VII.2.1 Photolysis of hydrogen peroxide in absence of acetic acid
....................................................................................... 84
VII.2.2 Photolysis of hydrogen peroxide in the presence of acetic
acid ....................................................................................... 85
VII.3 Photocatalytic decomposition of H2O2 ............................... 87
VII.3.1 Homogeneous photocatalytic decomposition of H2O2 ... 87
VII.3.2 Heterogeneous photocatalytic decomposition of H2O2 .. 88
VII.4 Photocatalytic decomposition of acetic acid ...................... 91
VII.5 Catalyst samples for photo-Fenton tests............................. 93
VII.6 Catalytic photo-Fenton oxidation....................................... 93
VII.6.1 Homogeneous photo-Fenton oxidation.......................... 93
VII.6.2 Heterogeneous photo-Fenton oxidation ........................ 95
VII.6.2.1 Heterogeneous photo-Fenton oxidation on LaMnO3
(3.67%) ................................................................................... 95
VII.6.2.2 Heterogeneous photo-Fenton oxidation on Pt/LaMnO3
................................................................................... 97
VII.6.2.3 Heterogeneous photo-Fenton oxidation on LaFeO3
(2.24%) ................................................................................... 98
VII.6.2.4 Heterogeneous photo-Fenton oxidation on LaCuO3.. 99
VII.6.2.5 Heterogeneous photo-Fenton oxidation on LaCoO3 100
VII.6.2.6 Heterogeneous photo-Fenton oxidation on LaNiO3 101
VII.6.2.7 Heterogeneous photo-Fenton oxidation on LnFeO3
(48%) ................................................................................. 103
VII.6.2.8 Heterogeneous photo-Fenton oxidation on LnFeO3
(88%) ................................................................................. 103
VII.6.2.9 Heterogeneous photo-Fenton oxidation on Pt/Ln2O3 ....
................................................................................. 104
VII.6.2.10 Heterogeneous photo-Fenton oxidation on Pd/Ln2O3 ...
................................................................................. 105
VII.7 Thermal analysis .............................................................. 106
VII.8 Catalytic activity comparison........................................... 107
VII.8.1 Heterogeneous vs homogeneous Photo-Fenton........... 107
VIII Experimental results: photo-Fenton oxidation of acetic acid
on LaMnO3, LaFeO3 and LnFeO3 .......................................................... 109
VIII.1.1 Comparison of catalytic activity of the monolith with
respect to powder catalysts ............................................................... 109
VIII.1.2 Effect of mass catalyst ............................................. 112
VIII.1.3 Effect of pH.............................................................. 113
VIII.1.4 Effect of H2O2 concentration ................................... 116
VIII.1.5 Effect of dosage of H2O2 .......................................... 117
VIII.2 Leaching test .................................................................... 121
IX Heterogeneous photo-Fenton: reaction mechanism hypothesis
.................................................................................................. 123

III
X Experimental results: photo-Fenton oxidation of alcohols on
LaMeO3 ..................................................................................................... 129
X.1 Photolysis.............................................................................. 129
X.1.1 Photolysis of ethanol.................................................... 129
X.1.2 Photolysis of methanol................................................. 130
X.2 Catalytic photo-Fenton oxidation of ethanol on LaMnO3
(3.67%) .............................................................................................. 131
X.3 Catalytic photo-Fenton oxidation of methanol on LaMnO3
(3.67%) .............................................................................................. 131
XI Experimental results: photo-Fenton oxidation of synthetic
winery wastewater on LaMeO3 ............................................................... 133
XI.1 Photolysis of synthetic winery wastewaters (red wine)........ 135
XI.2 Photolysis of synthetic winery wastewaters (red wine not
containing sulphites) .............................................................................. 137
XI.3 Catalytic photo-Fenton oxidation of synthetic winery
wastewaters (red wine) on LaMnO3 (3.67%)......................................... 139
XI.4 Catalytic photo-Fenton oxidation of synthetic winery
wastewaters (local red wine not containing sulphites) on LaMnO3 (3.67%)
.............................................................................................. 141
XI.5 Catalytic photo-Fenton oxidation of the synthetic winery
wastewaters (red wine local not containing sulphites) on LnFeO3 (48%) ...
.............................................................................................. 142
XI.6 Effect of dosage of H2O2 (red wine local not containing
sulphites) .............................................................................................. 144
XI.7 Leaching test......................................................................... 146
XII Conclusions.............................................................................. 149
XIII References ................................................................................ 151

IV
Index of figures

Figure 1. Line graph of the evolution of contamination levels (on an


arbitrary scale) of natural waters in countries with sustainable
development. From left to right the lines represent municipal faecal
waste drainage, industrial effluents, nutrients and micro-pollutants.
Contamination levels due to environmental problems increase until a
solution is found and subsequently decrease......................................... 2
Figure 2. Line graph of contamination levels (on an arbitrary scale) of
natural waters in non-sustainable developed countries. From left to
right the lines represent municipal faecal waste drainage, industrial
effluents, nutrients and micro-pollutants. Environmental problems have
increased with no solution yet having been found................................. 3
Figure 3. Mechanism of electrochemical processes....................................... 6
Figure 4. The water photolysis reaction......................................................... 7
Figure 5. Oxidation power of selected oxidizing species. .............................. 9
Figure 6. Suitability of water treatment technologies according to COD
contents (Andreozzi et al., 1999). ........................................................ 11
Figure 7. Oxidizable compounds by hydroxyl radicals (Bigda, 1995). ........ 14
Figure 8. Mechanism of Fenton reaction. .................................................... 15
Figure 9. Mechanism of photo-Fenton reaction........................................... 15
Figure 10. Proportion of Fe2+ and the species in equilibrium with it at 25°C.
............................................................................................................. 16
Figure 11. Concentration of Fe3+ in solution in relation to the pH at 25°C. 17
Figure 12. Proportion of Fe3+ and the existing species in equilibrium with it
at 25°C................................................................................................. 17
Figure 13. The Fenton Reaction: scheme of mechanism.............................. 18
Figure 14. Reaction of ferrous ion combined with hydrogen peroxide. ....... 19
Figure 15. The photo-Fenton Reaction: scheme of mechanism. .................. 19
Figure 16. Photo-induced reactions. ............................................................ 20
Figure 17. TGAQ500 Thermogravimetric Analyzer..................................... 30
Figure 18. SDTQ600 Simultaneous DSC/TGA............................................. 30
Figure 19. Pfieffer Vacuum Benchtop Thermostar mass spectrometer........ 31
Figure 20. TG and DTG curves.................................................................... 32
Figure 21. Costech Sorptometer 1040.......................................................... 33

V
Figure 22. Dispersive MicroRaman (Invia, Renishaw). ............................... 34
Figure 23. Laboratory apparatus for catalytic Fenton oxidation................. 36
Figure 24. Laboratory apparatus for the catalytic photo-Fenton oxidation.37
Figure 25. Sealed stainless-steel batch photoreactor................................... 37
Figure 26. Components of the sealed stainless-steel batch photoreactor. ... 38
Figure 27. The ultraviolet spectrum of the UV lamp used............................ 39
Figure 28. Set-up of experiment for total organic carbon analysis.............. 40
Figure 29. Y structure. .................................................................................. 44
Figure 30. X-Ray diffraction spectra of FeY and HY catalysts..................... 46
Figure 31. Conversion as a function of time of homogeneous catalytic
reaction with acetic acid at T=25°C. Experimental conditions:
pHt=0=2.67, mcatalyst= 1.426 g............................................................... 47
Figure 32. Conversion as a function of time of a heterogeneous catalytic
reaction with liming solution at T=25°C. Experimental conditions:
pHt=0=2.0, mcatalyst= 0.379 g................................................................. 48
Figure 33. Conversion as a function of time of reaction in the case of the FeY
catalyst at T=25°C. Experimental conditions: pHt=0=2.67, mcatalyst=
0.170 g. ................................................................................................ 49
Figure 34. Conversion as a function of time of reaction in the case of the FeY
catalyst at T=70°C. Experimental conditions: pHt=0=2.67, mcatalyst=
0.170 g. ................................................................................................ 50
Figure 35. Thermal analysis performed on FeY sample before catalytic
activity test. .......................................................................................... 51
Figure 36. Thermal analysis performed on FeY sample after catalytic activity
test at T=25°C in air flow.................................................................... 52
Figure 37. Thermal analysis performed on FeY sample after catalytic activity
test at T=70°C in air flow.................................................................... 52
Figure 38. Leaching test on FeY after catalytic test at T=70°C................... 53
Figure 39. Perovskite structure. ................................................................... 55
Figure 40. Thermal analysis of perovskite precursors. ................................ 57
Figure 41. X-ray diffraction patterns of cordierite carrier and supported
perovskite catalysts. P perovskite peaks; C, lanthanum oxy-carbonate
peaks. ................................................................................................... 58
Figure 42. SEM data on a carrier and on supported catalysts: (a) carrier, (b)
carrier+Ln2O3, (c) carrier+LaMnO3, (d) carrier+Ln2O3+LaMnO3. .. 59
Figure 43. Raman spectra of LaMnO3 (3.67 %) and LaMnO3 with Pt
samples. ............................................................................................... 60
Figure 44. Raman spectra of LaFeO3 monolith and LaFeO3 powder........... 61
Figure 45. Band-gap calculus from the DR–UV–vis spectra of LaMnO3..... 62
Figure 46. Band-gap calculus from the DR–UV–vis spectra of Pt/LaMnO3..
............................................................................................................. 62
Figure 47. Band-gap calculus from the DR–UV–vis spectra of LaFeO3...... 63
Figure 48. Band-gap calculus from the DR–UV–vis spectra of LnFeO3
(48%). .................................................................................................. 63

VI
Figure 49. Band-gap calculus from the DR–UV–vis spectra of LnFeO3
(88%). .................................................................................................. 64
Figure 50. Catalytic decomposition of H2O2 with LaMnO3 (2.57%).
Experimental conditions: pHt=o=5.3, mcatalyst= 19 g, [H2O2]t=0= 0.083
mol/l..................................................................................................... 66
Figure 51. Catalytic decomposition of H2O2 with LnFeO3 (88%).
Experimental conditions: pHt=o=5.4, mcatalyst= 15 g, [H2O2]t=0= 0.083
mol/l..................................................................................................... 66
Figure 52. Total organic carbon removal and H2O2 conversion as a function
of time of reaction in the case of LaMnO3 (3.67%) catalyst at T=25°C.
Experimental conditions: pHt=o=3.9, mcatalyst= 4.9 g, [H2O2]t=0= 0.083
mol/l..................................................................................................... 67
Figure 53. Total organic carbon removal and H2O2 conversion as a function
of time of reaction in the case of LaMnO3 (3.67%) catalyst at T=25°C.
Experimental conditions: pHt=o=3.9, mcatalyst= 4.9 g, [H2O2]t=0= 0.167
mol/l..................................................................................................... 68
Figure 54. Total organic carbon removal and H2O2 conversion as a function
of time of reaction in the case of Pt/LaMnO3 catalyst at T=25°C.
Experimental conditions: pHt=o=3.9, mcatalyst= 6.0 g, [H2O2]t=0= 0.083
mol/l..................................................................................................... 69
Figure 55. Total organic carbon removal as function of time of reaction in
the case of Pt/LaMnO3 catalyst at T=25°C. Experimental conditions:
pHt=o=3.9, mcatalyst= 6.0 g, [H2O2]t=0= 0.167 mol/l. ............................ 70
Figure 56. Total organic carbon removal and H2O2 conversion as a function
of time of reaction in the case of LaFeO3 catalyst at T=25°C.
Experimental conditions: pHt=o=3.9, mcatalyst= 5.4 g, [H2O2]t=0= 0.083
mol/l..................................................................................................... 71
Figure 57. Total organic carbon removal and H2O2 conversion as a function
of time of reaction in the case of LaFeO3 catalyst at T=25°C.
Experimental conditions: pHt=o=3.9, mcatalyst= 5.4 g, [H2O2]t=0= 0.167
mol/l..................................................................................................... 72
Figure 58. Total organic carbon removal and H2O2 conversion as a function
of time of reaction in the case of LaCuO3 catalyst at T=25°C.
Experimental conditions: pHt=o=3.9, mcatalyst= 6.4 g, [H2O2]t=0= 0.083
mol/l..................................................................................................... 73
Figure 59. Total organic carbon removal and H2O2 conversion as a function
of time of reaction in the case of LaCuO3 catalyst at T=25°C.
Experimental conditions: pHt=o=3.9, mcatalyst= 5.4 g, [H2O2]t=0= 0.167
mol/l..................................................................................................... 74
Figure 60. Total organic carbon removal and H2O2 conversion as a function
of time of reaction in the case of LaNiO3 catalyst at T=25°C.
Experimental conditions: pHt=o=3.9, mcatalyst= 6.0 g, [H2O2]t=0= 0.083
mol/l..................................................................................................... 75

VII
Figure 61. Total organic carbon removal and H2O2 conversion as a function
of time of reaction in the case of LaNiO3 catalyst at T=25°C.
Experimental conditions: pHt=o=3.9, mcatalyst= 6.0 g, [H2O2]t=0= 0.167
mol/l. .................................................................................................... 76
Figure 62. Total organic carbon removal and H2O2 conversion as a function
of time of reaction in the case of LaCoO3 catalyst at T=25°C.
Experimental conditions: pHt=o=3.9, mcatalyst= 5.4 g, [H2O2]t=0= 0.087
mol/l. .................................................................................................... 77
Figure 63. Total organic carbon removal and H2O2 conversion as a function
of time of reaction in the case of the LaCoO3 catalyst at T=25°C.
Experimental conditions: pHt=o=3.9, mcatalyst= 5.4 g, [H2O2]t=0= 0.167
mol/l. .................................................................................................... 78
Figure 64. Catalytic photo-Fenton oxidation in nitrogen stream on LaMnO3
(3.67%). Experimental conditions: V tot.: 100 ml; mcatalyst= 4.9 g;
C0CH3COOH= 0.021 mol/l; C0H2O2= 0.083 mol/l; P= 1 atm; T=25°C;
pH=3.9, QN2= 250 Ncc/min................................................................. 82
Figure 65. Carbon dioxide concentration formed during catalytic photo-
Fenton oxidation in nitrogen stream on LaMnO3 (3.67%).................. 83
Figure 66. Photolysis of H2O2 in absence of acetic acid. Experimental
conditions: V tot.: 100 ml; C0H2O2= 0.167 mol/l; P= 1 atm; T=25°C;
pH=3.9................................................................................................. 84
Figure 67. Photolysis of H2O2 in the presence of acetic acid. Experimental
conditions: V tot.: 100 ml; H2O2/CH3COOH= 4; C0H2O2= 0.083 mol/l;
P= 1 atm; T=25°C; pH=3.9................................................................ 85
Figure 68. Photolysis of H2O2 in the presence of acetic acid. Experimental
conditions: V tot.: 100 ml; H2O2/CH3COOH= 8; C0H2O2= 0.167 mol/l;
P= 1 atm; T=25°C; pH=3.9................................................................ 86
Figure 69. Photocatalytic decomposition of H2O2 with Fe2(C2O4)3.
Experimental conditions: V tot.: 100 ml; mcatalyst= 0.7 g; C0H2O2= 0.083
mol/l; P= 1 atm; T=25°C; pH=3.9. .................................................... 87
Figure 70. Photocatalytic decomposition of H2O2 with Fe2(C2O4)3.
Experimental conditions: V tot.: 100 ml; mcatalyst= 0.7 g; C0H2O2= 0.167
mol/l; P= 1 atm; T=25°C; pH=3.9. .................................................... 88
Figure 71. Photocatalytic decomposition of H2O2 with LaMnO3 (3.67%).
Experimental conditions: V tot.: 100 ml; mcatalyst= 4.9 g; C0H2O2= 0.083
mol/l; P= 1 atm; T=25°C; pH=3.9. .................................................... 89
Figure 72. Photocatalytic decomposition of H2O2 with LaMnO3 (3.67%).
Experimental conditions: V tot.: 100 ml; mcatalyst= 4.9 g; C0H2O2= 0.167
mol/l; P= 1 atm; T=25°C; pH=3.9. .................................................... 89
Figure 73. Photocatalytic decomposition of H2O2 with Pt/LaMnO3.
Experimental conditions: V tot.: 100 ml; mcatalyst= 6.0 g; C0H2O2= 0.083
mol/l; P= 1 atm; T=25°C; pH=3.9. .................................................... 90

VIII
Figure 74. Photocatalytic decomposition of H2O2 with Pt/LaMnO3.
Experimental conditions: V tot.: 100 ml; mcatalyst= 6.0 g; C0H2O2= 0.167
mol/l; P= 1 atm; T=25°C; pH=3.9. .................................................... 91
Figure 75. Photocatalytic decomposition of acetic acid with LaMnO3
(3.67%). Experimental conditions: V tot.: 100 ml; mcatalyst= 4.9 g;
TOCt=0= 250 ppm; P= 1 atm; T=25°C; pH=3.9. ............................... 92
Figure 76. Photocatalytic decomposition of acetic acid with LaMnO3
(3.67%). Experimental conditions: V tot.: 100 ml; mcatalyst= 4.9 g;
TOCt=0= 500 ppm; P= 1 atm; T=25°C; pH=3.9. ............................... 92
Figure 77. Homogeneous photo-Fenton with Fe2(C2O4)3. Experimental
conditions: V tot.: 100 ml; mcatalyst= 0.7 g; C0CH3COOH= 0.021 mol/l;
C0H2O2= 0.083 mol/l; P= 1 atm; T=25°C; pH=3.9. ............................ 94
Figure 78. Heterogeneous photo-Fenton with LaMnO3 (3.67%).
Experimental conditions: V tot.: 100 ml; mcatalyst= 4.9 g; C0CH3COOH=
0.021 mol/l; C0H2O2= 0.083 mol/l; P= 1 atm; T=25°C; pH=3.9......... 95
Figure 79. Heterogeneous photo-Fenton with LaMnO3 (3.67%).
Experimental conditions: V tot.: 100 ml; mcatalyst= 4.9 g; C0CH3COOH=
0.021 mol/l; C0H2O2= 0.167 mol/l; P= 1 atm; T=25°C; pH=3.9......... 96
Figure 80. Heterogeneous photo-Fenton with LaMnO3 with Pt. Experimental
conditions: V tot.: 100 ml; mcatalyst= 6.0 g; C0CH3COOH= 0.021 mol/l;
C0H2O2= 0.083 mol/l; P= 1 atm; T=25°C; pH=3.9. ............................ 97
Figure 81. Heterogeneous photo-Fenton with LaMnO3 with Pt. Experimental
conditions: V tot.: 100 ml; mcatalyst= 6.0 g; C0CH3COOH= 0.021 mol/l;
C0H2O2= 0.167 mol/l; P= 1 atm; T=25°C; pH=3.9. ............................ 98
Figure 82. Heterogeneous photo-Fenton with LaFeO3 (2.24%). Experimental
conditions: V tot.: 100 ml; mcatalyst= 5.4 g; C0CH3COOH= 0.021 mol/l;
C0H2O2= 0.083 mol/l; P= 1 atm; T=25°C; pH=3.9. ............................ 99
Figure 83. Heterogeneous photo-Fenton with LaCuO3. Experimental
conditions: V tot.: 100 ml; mcatalyst= 6.4 g; C0CH3COOH= 0.021 mol/l;
C0H2O2= 0.083 mol/l; P= 1 atm; T=25°C; pH=3.9. .......................... 100
Figure 84. Heterogeneous photo-Fenton with LaCoO3. Experimental
conditions: V tot.: 100 ml; mcatalyst= 5.4 g; C0CH3COOH= 0.021 mol/l;
C0H2O2= 0.083 mol/l; P= 1 atm; T=25°C; pH=3.9. .......................... 101
Figure 85. Heterogeneous photo-Fenton with LaNiO3. Experimental
conditions: V tot.: 100 ml; mcatalyst= 6.0 g; C0CH3COOH= 0.021 mol/l;
C0H2O2= 0.083 mol/l; P= 1 atm; T=25°C; pH=3.9. .......................... 102
Figure 86. Heterogeneous photo-Fenton with LnFeO3 (48%). Experimental
conditions: V tot.: 100 ml; mcatalyst= 14.0 g; C0CH3COOH= 0.021 mol/l;
C0H2O2= 0.083 mol/l; P= 1 atm; T=25°C; pH=3.9. .......................... 103
Figure 87. Heterogeneous photo-Fenton with LnFeO3 (88%). Experimental
conditions: V tot.: 100 ml; mcatalyst= 15.3 g; C0CH3COOH= 0.021 mol/l;
C0H2O2= 0.083 mol/l; P= 1 atm; T=25°C; pH=3.9. .......................... 104

IX
Figure 88. Heterogeneous photo-Fenton with Pt/Ln2O3. Experimental
conditions: V tot.: 100 ml; mcatalyst= 4.4 g; C0CH3COOH= 0.021 mol/l;
C0H2O2= 0.083 mol/l; P= 1 atm; T=25°C; pH=3.9. .......................... 105
Figure 89. Heterogeneous photo-Fenton with Pd/Ln2O3. Experimental
conditions: V tot.: 100 ml; mcatalyst= 4.4 g; C0CH3COOH= 0.021 mol/l;
C0H2O2= 0.083 mol/l; P= 1 atm; T=25°C; pH=3.9. .......................... 106
Figure 90. Thermal analysis performed on the LaMnO3 (2.69%) sample
before and after the catalytic activity test.......................................... 107
Figure 91. Heterogeneous vs homogeneous photo-Fenton. ....................... 108
Figure 92. Comparison of catalytic activity of the monolith LaMnO3 (2.69%)
with respect to powdered catalyst. Experimental conditions: V tot.: 100
ml; mcatalyst= 6.0 g; C0CH3COOH= 0.021 mol/l; C0H2O2= 0.083 mol/l; P= 1
atm; T=25°C; pH=3.9....................................................................... 110
Figure 93. Comparison of catalytic activity of the monolith LaMnO3 (2.69%)
with respect to powder not supported. Experimental conditions: V tot.:
100 ml; mcatalyst (monolith)= 5.0 g; mcatalyst (powder)= 0.184 g; C0CH3COOH=
0.021 mol/l; C0H2O2= 0.083 mol/l; P= 1 atm; T=25°C; pH=3.9. ...... 111
Figure 94. Comparison of catalytic activity of the monolith LaFeO3 with
respect to powder. Experimental conditions: V tot.: 100 ml; mcatalyst
0
(monolith)= 6.0 g; mcatalyst (powder)= 0.122 g; C CH3COOH= 0.021 mol/l;
0
C H2O2= 0.083 mol/l; P= 1 atm; T=25°C; pH=3.9. .......................... 112
Figure 95. Comparison of catalytic activity of the monolith LaMnO3 (2.57%)
with different mass. Experimental conditions: V tot.: 100 ml; mcatalyst=
14.0 g – 4.9 g; C0CH3COOH= 0.021 mol/l; C0H2O2= 0.083 mol/l; P= 1
atm; T=25°C; pH=3.9....................................................................... 113
Figure 96. Effect of pH reaction on catalytic activity of monolith LaMnO3
(3.67%). Experimental conditions: V tot.: 100 ml; mcatalyst= 4.9 g;
C0CH3COOH= 0.021 mol/l; C0H2O2= 0.083 mol/l; P= 1 atm; T=25°C. . 114
Figure 97. Effect of pH reaction on catalytic activity of monolith LaMnO3
(2.69%). Experimental conditions: V tot.: 100 ml; mcatalyst= 5.6 g;
C0CH3COOH= 0.021 mol/l; C0H2O2= 0.083 mol/l; P= 1 atm; T=25°C. . 115
Figure 98. Comparison of catalitic activity on LaMnO3 (3.67%) on changing
H2O2. concentration........................................................................... 116
Figure 99. Effect of dosage of H2O2 on the catalytic activity of LaMnO3
(3.67%). Experimental conditions: V tot.: 100 ml; mcatalyst= 4.9 g;
C0CH3COOH= 0.021 mol/l; C0H2O2= 0.014 mol/l; CH2O2/t= 0.009 M/h; P=
1 atm; T=25°C................................................................................... 117
Figure 100. Effect of dosage of H2O2 on the catalytic activity of LnFeO3
(48%). Experimental conditions: V tot.: 100 ml; mcatalyst= 14 g;
C0CH3COOH= 0.021 mol/l; C0H2O2= 0.012 mol/l; CH2O2/t= 0.006 M/h; P=
1 atm; T=25°C................................................................................... 118
Figure 101. Effect of dosage of H2O2 on the catalytic activity of LnFeO3
(88%). Experimental conditions: V tot.: 100 ml; mcatalyst= 15.3 g;

X
C0CH3COOH= 0.021 mol/l; C0H2O2= 0.022 mol/l; CH2O2/t= 0.021 M/h; P=
1 atm; T=25°C................................................................................... 118
Figure 102. Photolysis of hydrogen peroxide............................................. 124
Figure 103. Catalytic decomposition of H2O2. ........................................... 125
Figure 104. Illustration of the photo-Fenton process................................. 127
Figure 105. Photolysis of ethanol. Experimental conditions: V tot.: 100 ml;
H2O2/C2H5OH= 2; C0H2O2= 0.042 mol/l; C0C2H5OH= 0.021; P= 1 atm;
T=25°C; pH=6.5. .............................................................................. 130
Figure 106. Photolysis of methanol. Experimental conditions: V tot.: 100 ml;
H2O2/CH3OH= 1; C0H2O2= 0.042 mol/l; C0CH3OH= 0.021 mol/l; P= 1
atm; T=25°C; pH=5.5....................................................................... 130
Figure 107. Catalytic photo-Fenton oxidation of ethanol on LaMnO3
(3.67%). Experimental conditions: V tot.: 100 ml; H2O2/C2H5OH= 2;
C0H2O2= 0.042 mol/l; C0C2H5OH= 0.021; P= 1 atm; T=25°C; pH=6.5.
........................................................................................................... 131
Figure 108. Catalytic photo-Fenton oxidation of methanol on LaMnO3
(3.67%). Experimental conditions: V tot.: 100 ml; H2O2/CH3OH= 1;
C0H2O2= 0.042 mol/l; C0CH3OH= 0.021 mol/l ; P= 1 atm; T=25°C;
pH=5.5. ............................................................................................. 132
Figure 109. Photolysis of synthetic winery wastewaters obtained by diluting
commercial red wine. Experimental conditions: V tot.: 100 ml;
H2O2/TOCwine= 1; C0H2O2= 0.042 mol/l; P= 1 atm; T=25°C; pH=4.2.
........................................................................................................... 135
Figure 110. Photolysis of synthetic winery wastewaters obtained by diluting
commercial red wine. Experimental conditions: V tot.: 100 ml;
H2O2/TOCwine= 2; C0H2O2= 0.042 mol/l; P= 1 atm; T=25°C; pH=4.2.
........................................................................................................... 136
Figure 111. Photolysis of synthetic winery wastewaters obtained by diluting
commercial red wine not containing sulphites. Experimental
conditions: V tot.: 100 ml; H2O2/TOCwine= 1; C0H2O2= 0.042 mol/l; P=
1 atm; T=25°C; pH=4.2.................................................................... 137
Figure 112. Photolysis of synthetic winery wastewaters obtained by diluting
commercial red wine not containing sulphites. Experimental
conditions: V tot.: 100 ml; H2O2/TOCwine= 2; C0H2O2= 0.084 mol/l; P=
1 atm; T=25°C; pH=4.2.................................................................... 138
Figure 113. Catalytic photo-Fenton oxidation of synthetic winery
wastewaters obtained by diluting commercial red wine on LaMnO3
(3.67%). Experimental conditions: V tot.: 100 ml; H2O2/TOCwine= 1;
C0H2O2= 0.042 mol/l; P= 1 atm; T=25°C; pH=4.2. .......................... 139
Figure 114. Catalytic photo-Fenton oxidation of synthetic winery
wastewaters obtained by diluting commercial red wine on LaMnO3
(3.67%). Experimental conditions: V tot.: 100 ml; H2O2/TOCwine= 2;
C0H2O2= 0.042 mol/l; P= 1 atm; T=25°C; pH=4.2. .......................... 140

XI
Figure 115. Catalytic photo-Fenton oxidation of synthetic winery
wastewaters obtained by diluting local red wine on LaMnO3 (3.67%).
Experimental conditions: V tot.: 100 ml; H2O2/TOCwine= 1; C0H2O2=
0.042 mol/l; P= 1 atm; T=25°C; pH=4.2. ........................................ 141
Figure 116. Catalytic photo-Fenton oxidation of synthetic winery
wastewaters obtained by diluting local red wine on LaMnO3 (3.67%).
Experimental conditions: V tot.: 100 ml; H2O2/TOCwine= 2; C0H2O2=
0.084 mol/l; P= 1 atm; T=25°C; pH=4.2. ........................................ 142
Figure 117. Catalytic photo-Fenton oxidation of synthetic winery
wastewaters obtained by diluting local red wine on LnFeO3 (48%).
Experimental conditions: V tot.: 100 ml; H2O2/TOCwine= 1; C0H2O2=
0.042 mol/l; P= 1 atm; T=25°C; pH=4.2. ........................................ 143
Figure 118. Effect of dosage of H2O2 on the catalytic activity of LaMnO3
(3.67%). Experimental conditions: V tot.: 100 ml; mcatalyst= 4.9 g;
TOC0wine= 500 mg/l; C0H2O2= 0.006 mol/l; CH2O2/t= 0.009 M/h; P= 1
atm; T=25°C; pH=4.2....................................................................... 144
Figure 119. Effect of dosage of H2O2 on the catalytic activity of LnFeO3
(48%). Experimental conditions: V tot.: 100 ml; mcatalyst= 14 g;
TOC0wine= 500 mg/l; C0H2O2= 0.006 mol/l; CH2O2/t= 0.012 M/h; P= 1
atm; T=25°C; pH=4.2....................................................................... 145

XII
Index of tables

Table 1. Characteristic of the UV lamp utilised........................................... 38


Table 2. Procedure of ion exchange for samples. ........................................ 44
Table 3. Microporous volume of HY and FeY.............................................. 45
Table 4. List of perovskite-based catalysts characterised............................ 56
Table 5. pH and oxygen dissolved values for the catalytic decomposition of
hydrogen peroxide. .............................................................................. 67
Table 6. Metal ion analysis of the some catalyst used for the catalytic Fenton
reaction................................................................................................ 79
Table 7. List of catalysts tested. ................................................................... 93
Table 8. Comparison of hydrogen peroxide consumption of the photo-Fenton
of LaMnO3 (3.67%) with dosage of H2O2 with respect to the
photo/LaMnO3 system with H2O2/CH3COOH=4. ............................. 119
Table 9. Comparison of hydrogen peroxide consumption of the photo-Fenton
of LnFeO3 (48%) with dosage of H2O2 with respect to the
photo/LnFeO3 system with H2O2/CH3COOH=4................................ 120
Table 10. Comparison of hydrogen peroxide consumption of the photo-
Fenton of LnFeO3 (88%) with dosage of H2O2 with respect to the
photo/LnFeO3 system with H2O2/CH3COOH=4................................ 120
Table 11. Metal ion analysis of the some catalysts used for the catalytic
photo-Fenton reaction. ...................................................................... 121
Table 12. Comparison of hydrogen peroxide consumption of photo-Fenton of
LaMnO3 (3.67%) with dosage of H2O2 with respect to the
photo/LaMnO3 system with H2O2/ TOCwine =2.................................. 145
Table 13. Comparison of hydrogen peroxide consumption of the photo-
Fenton of LnFeO3 (48%) with dosage of H2O2 with respect to the
photo/LnFeO3 system with H2O2/ TOCwine =1................................... 146
Table 14. Metal ion analysis of the some catalysts used for the catalytic
photo-Fenton reaction of synthetic winery wastewater..................... 147

XIII
Abstract

Advanced oxidation processes (AOPs) are an attractive alternative for


treating wastewater containing organic substances. Currently, AOPs widely
studied are the Fenton process (Fe2+/H2O2) and photolysis (H2O2/UV). In the
development of heterogeneous catalysts for Fenton wastewater treatment,
various powder formulations have been investigated. Recent studies have
also been devoted to UV-enhanced Fenton process. Limitations due to the
use of homogeneous catalysts, such as limited pH range, production of Fe
containing sludge, and deactivation could be overcome by heterogeneous
catalysts.
In this work, an innovative application of monolith structured perovskite
catalysts in heterogeneous photo-Fenton reaction of acetic acid, methanol
and ethanol, chosen as model pollutants, and of winery wastewater has been
reported.
A recirculating stainless-steel photocatalytic sealed batch reactor, useful
to test several catalysts both in powder and in a structured form has been
specifically developed
It has been found that, from values of TOC removal and carbon dioxide
evolved in gas phase, the total carbon mass balance was closed to 100%,
indicating the complete mineralization of the acetic acid, without formation
of noxious by-products.
The results showed that use of a heterogeneous structured catalyst in the
photo-Fenton reaction greatly improves TOC removal with respect to
homogeneous ones and leads to better use of H2O2.
Among Fe-zeolites, Fe-, Mn-, Co-, Ni-, Cu-based perovskites,
lanthanides oxides, in the presence or in the absence of low amounts of Pd
and Pt, best performances were shown by LaMnO3 and LnFeO3 structured
catalysts.
The study then focused on Mn and Fe perovskites, by optimising
operative process conditions with resulting low H2O2 initial concentrations,
pH=6, catalyst/wastewater mass ratio of 5 wt%.
The use of perovskite structured catalysts also leads to a widened pH
range of operation.
It has been shown that in photo-Fenton processes, efficiency depends on
optimal dosage of H2O2. Lower H2O2 consumption with total TOC removal
within 7 hours can be reached by H2O2 step addition.
A reaction mechanism, involving H2O2 and CH3COOH competitive
adsorption on catalyst surface and the oxidation of adsorbed acetic acid by
UV-generated hydroxyls radicals, has been hypothesized.
Finally, it has been evidenced that photocatalytic advanced oxidation
based on H2O2 is an appropriate purification treatment for winery
wastewaters.
I Introduction

One of the characteristics that best defines today’s society in what are
known as developed countries is the production of waste products. There is
practically no human activity that does not produce waste products and in
addition there is a direct relationship between the standard of living in a
society or country and the amount of waste products produced.
Approximately 23% of the world’s population live in developed countries,
consume 78% of the resources and produce 82% of the waste products
(Blanco et al., 1996). In addition, it has to be pointed out that the volume of
residual waste increases in an exceptional way with regards to a country’s
level of industrialisation. At present, there are some five million known
substances registered, of which approximately 70,000 are widely used
worldwide, and it is estimated that 1,000 new chemical substances are added
to the list each year.
The need for sustainable growth is countered by the reality of
demographic growth.
Many countries are experiencing a period of non-sustainable growth, with
very variable macroeconomic achievements in various countries. Even in the
case where some countries have achieved beneficial macroeconomic
progress, these achievements are not reflected in the standard of living and
quality of life of large sections of the population.
These large contrasts are reflected in the problems related to the rational
management of water, which cannot be dealt with unilaterally, but by many
different procedures.
A recent publication (Schertenleib et al., 2000) contains a general
description of the problems that societies have had to face regarding water
use as society evolved. Countries with sustainable development have, one by
one, confronted the problems related to biological contamination, icuding
levels of heavy metals, intensive use of nutrients, and organic contaminants
at very low levels. Water disinfection, the treatment of effluents before being
discharged into water systems, the limitation and substitution of nitrates and
phosphates in products that are used on a massive scale and developments in
analytical chemistry and in ecotoxicology are examples of some of the
“tools” used to combat these problems. The evolution of contamination
Chapter I

levels (on an arbitrary scale) of natural waters in countries with sustainable


development is shown in Figure 1. It should be noted that the time needed to
resolve each problem as it arises, has become shorter over the decades.

Figure 1. Line graph of the evolution of contamination levels (on an


arbitrary scale) of natural waters in countries with sustainable development.
From left to right the lines represent municipal faecal waste drainage,
industrial effluents, nutrients and micro-pollutants. Contamination levels
due to environmental problems increase until a solution is found and
subsequently decrease.
In contrast, countries with non-sustainable development are represented
in Figure 2. There is no doubt that many developing countries can be
included in this category, or even in more complicated situations with more
primitive stages of development. The problems deriving from the
toxicological effects of organic compounds, active at very low levels, must
be resolved at the same time as water disinfection for rural communities. It is
clear that innovative procedures are needed to deal with a wide range of
problems which vary notably in the scale of application and the complexity
of the problems themselves (Blesa, 2001).
Up until relatively recently, the discharging of waste into the environment
was the only way of eliminating it, until the self-cleaning capacity of the
environment was no longer sufficient. Permitted levels of pollution have
been vastly exceeded, causing such environmental contamination that our
natural resources cannot be employed for certain uses because their
characteristics have been altered. The main problem stems from waste
coming from industry and agriculture, along with environmental
contamination caused by the population.

2
Introduction

Figure 2. Line graph of contamination levels (on an arbitrary scale) of


natural waters in non-sustainable developed countries. From left to right the
lines represent municipal faecal waste drainage, industrial effluents,
nutrients and micro-pollutants. Environmental problems have increased with
no solution yet having been found.
Phenols, pesticides, fertilizers, detergents and other chemical products are
disposed of untreated directly into the environment, by controlled or
uncontrolled discharging, and with no treatment strategy.
In this general context, it is very clear that the strategy to continue in the
search of solutions to this problem which is in sensitive growth, mainly in
developing countries, will concentrate on two fundamental aspects:
1. The development of appropriate methods for
decontamination of drinking, ground and surfaces waters.
2. The development of appropriate methods for wastewater
containing toxic or non-biodegradable compounds.

I.1 Removal of organic compounds

The treatment processes of different types of effluents to be used must


guarantee the elimination or recuperation of the pollutant in order to reach
the strict authorized levels for the discharge of these effluents. The levels of
pollutants allowed in discharge waters, are directly related to the type of
pollutant present in the effluent.
In general, the elimination of organic pollutants in an aqueous solution
need to undergo one or more basic treatment techniques (Weber et al.,
1986), (Chuang et al., 1992): chemical oxidation, air desorption, liquid-

3
Chapter I

liquid extraction, adsorption, inverse osmosis, ultra-filtration and biological


treatment. Depending on the compound present in the solution destructive
methods can be used such as, for example, chemical oxidation, incineration
or degradation, which allow efficient elimination of the pollutant from an
aqueous form. Non-destructive methods can also be used such as, liquid-
liquid extraction and absorption, that allow recuperation of the pollutant.
Application of one or other of the methods depends on concentration in the
effluent. It is necessary to choose the most adequate method according to the
characteristics of the concentration. For high concentrations of pollutants,
techniques such as incineration or certain chemical oxidation methods are
advisable. On the other hand for low concentrations of pollutants,
adsorption, membrane techniques, and other chemical oxidation methods are
suitable. The choice of one or other of the methods basically depends on the
cost of the process and other factors like the concentration and volume flow
of the effluent to be treated.
The most widely used treatment methods of organic compounds are
described below.

I.1.1 Incineration

Incineration is a useful method for small quantities of wastewater with


high pollutant concentration. However, it presents the disadvantage of
requiring large investments and also has high energy costs. The incinerators
normally used for this process are similar to those used for sludge or
industrial residues, and they can be horizontal, vertical or fluidized beds.
One fundamental economic aspect in the incineration of organic solutions is
the auxiliary fuel needed to maintain combustion. In the case of textile
industries, incineration has been used in the treatment of sludge from textile
wastewater and the ash is landfilled (Masselli et al., 1970).
Incineration can also be used to minimize the quantity of textile
wastewater.

I.1.2 Air stripping

Air stripping involves the transfer of volatile organics from a liquid phase
to the air phase by greatly increasing the air/water contact area. Typical
aeration methods include packed towers, diffusers, trays, and spray aeration.
This method has the advantage that it’s more established and more widely
understood than chemical oxidation. It can be accurately designed from
theory and experience without the need for design tests. If air emissions are
not regulated, air stripping is by far the simplest and cheapest solution for
the removal of volatile compounds from water. In the case of textile

4
Introduction

wastewater, air stripping used as pretreatment resulted in high solvent


removal (Kabdasli et al., 2000).

I.1.3 Adsorption onto activated carbon

Carbon adsorption is an advanced wastewater treatment method used for


the removal of recalcitrant organic compounds as well as residual amounts
of inorganic compounds such as nitrogen, sulfides, and heavy metals. This is
a separation method in which the contaminant is transferred from a water
phase, where it is dissolved, to the surface of active carbon where it is
accumulated for its subsequent extraction or destruction.
Adsorption onto activated carbon is widely used for wastewater
treatment. Thus, it is used in the control of colour and odours, in the removal
of organic compounds or trihalomethane precursors, to remove chlorine and
in general to remove toxic compounds.
This method has also been combined with others and significant
improvement has been obtained (Cañizares et al., 1999). Many studies have
been found in the literature regarding the treatment of textile wastewater by
means of activated carbon (Lin and Lai, 2000), (Yeh et al., 2002).
Most of them showed the high effectiveness of the carbon activated
adsorption process in the reduction of COD (Chemical Oxidation Demand)
and colour removal from textile wastewater.

I.1.4 Wet oxidation

In wet oxidation processes, organic and inorganic compounds are


oxidized in the aqueous phase with oxygen or air, at high pressure and high
temperature conditions. The temperature depends on the nature of the
compounds to be degraded, however it oscillates between 150 and 350ºC.
Pressure goes from 20 to 200 bar. COD removal ranges from 75 to 90% (Li
et al., 1991). The mechanism of wet oxidation has been deeply studied and
seems to take place by means of a free radical process. Among the
compounds that have been catalogued as readily oxidizable by means of wet
oxidation are aliphatic, aliphatic chlorides and aromatic compunds, which do
not contain halogenated functional groups such as phenols or anilines.
Compounds containing halogen and nitro functional groups have been found
to be difficult to be degraded by this method (Scott, 1997). Experimental
results indicate that over 90% removal of phenol or phenolic compounds can
be achieved in wet oxidation wastewater treatment. The activated sludge
process combined with wet oxidation, if appropriately operated, is capable of

5
Chapter I

drastically reducing COD concentration in high concentrated chemical


wastewater to meet safe discharge requirement (Lin and Chuang, 1994).

I.1.5 Electrochemical oxidation

The use of electrochemical oxidation for the destruction of organic


compounds in water solutions has been tried on bench and pilot plant scale
(Boudenne et al., 1996), (Brillas et al., 1998), but is not used commercially
because of high operating costs. One of the main advantages of
electrochemical processes is that electrons are released by or spent by the
electrodes, supplying a clean reactant, which does not increase the number of
chemical molecules involved in the process. Nevertheless, electrochemila
processes present some disadvantages, such as:
ƒ Electrochemical treatment is expensive in comparison with
other processes and the mechanism in water is complex.
ƒ The effluent must be conductor. If the stream to be treated does
not present good conductivity salt should be added.
Electrochemical oxidation of organic compounds is thermodynamically
favoured against the competitive reaction of oxygen production by oxidation
of water. However, the kinetics of oxidation of water is much faster than the
kinetics of oxidation of organic compounds, among other reasons because of
its higher concentration (Palau, 1998).
The mechanism of electrochemical processes involves three stages:
electrocoagulation, electroflotation and electrooxidation. (Figure 3):

Figure 3. Mechanism of electrochemical processes.


Anodic oxidation is generally considered to be a direct technique,
involving the direct transfer of an electron from the organic molecule to the
electrode, thus generating a cationic radical. The fate of the cationic radical,
the pH and the nature of the electrodes influence (in a decisive manner) the
products formed. Radical combinations have frequently been observed.
Many articles have also been published on the application of
electrochemical processes in textile industry wastewater treatment. In a large
number of these articles, the efficiency of this method for colour removal has
been proven (Lin and Peng 1994), (Vlyssides et al., 2000), (Zappi et al.,

6
Introduction

2000), (Gutierrez et al., 2001). It has also been used in combination with
coagulation to remove colour, turbidity and COD.

I.1.6 Photochemical processes

For the oxidation of organic pollutants, a series of researchers have


proposed direct photo-oxidation with ultraviolet light (Petersen et al. (1988).
However, there are a number of limitations to its use. The first being that the
organic compound to be eliminated must absorb light in competition with
other compounds in the effluent to be treated. The second is that organic
compounds generate a wide variety of photochemical reactions that can
produce products that are more complex for degradation. In addition, not all
the radiation emitted by the source of radiation is fully exploited, only the
radiation absorbed and only a part of this produces chemical changes. This
means that some reactions of photodegradation have very slow kinetics.
The addition of energy as radiation to a chemical compound is the
principle of photochemical processes. Molecules absorb this energy and
reach excited states with decay times long enough to take part in chemical
reactions.
A large number of studies (Legrini et al., 1993) deal with the degradation
of chemicals in water using Hg emission at 253.7 nm produced by low-
pressure mercury lamps. However, results showed that 253.7 nm irradiation
alone could not be used as an effective procedure for the removal of organic
substances from water. This method may be useful for the degradation of
substituted aromatic compunds, however it is totally inefficient for effective
removal of chlorinated aliphatics. It should be noted, however, that low-
pressure Hg lamps are quite efficient for water disinfection purposes.
Medium and high-pressure lamps, with a broader emission spectrum, have
been used more frequently for the degradation of contaminants. Medium-
pressure Hg lamps emit particularly strongly in the spectral region between
254 and 400 nm and are not only effective in generating hydroxyl radicals
from hydrogen peroxide or ozone, for example, but also by causing
electronic transitions in a large number of organic molecules.
In photochemical reactions, hydroxyl radicals may be generated by water
photolysis (Cervera et al., 1983) (Figure 4):

Figure 4. The water photolysis reaction.


Photolysis involves the interaction of light with molecules to bring about
their dissociation into fragments. This reaction is a poor source of radicals,
and in the reaction medium large quantity of reaction intermediates that
absorb part of the radiation are generated, which causes the photo-oxidation
7
Chapter I

kinetics of the contaminants to decrease considerably. This make the process


valid only for effluents with a low concentration of pollutants.
Photochemical treatment, although partially solving the problem of the
refractory compounds, has some negative aspects in its practical application,
such as the high cost of UV radiation production. Furthermore, not all the
emitted radiation is used, only the radiation absorbed, and only a fraction of
this radiation produces chemical changes. This means that some
photodegradation reactions have very low yields and slow kinetics.
To accelerate the process, other oxidants such as hydrogen peroxide
and/or ozone, metallic salts or semiconductors like TiO2 can be added,
giving rise to so-called Advanced Oxidation Processes. Instead of UV lamps,
solar light could be used as radiation energy to degrade some compounds.
No effect was observed during direct photolysis of NB with a 150-W
mercury-xenon lamp in the study carried out by (Lipczynska-Kochany
1992).

I.1.7 Biological oxidation

Biological treatment, generally by means of activated sludge (Wiesmann


and Putnaerglis 1986), (Givens et al., 1991) in adequate conditions (Wu et
al., 1994) has unquestionable advantages for the destruction of organic
compounds. However, many organic pollutants cannot be effectively
eliminated by biological oxidation in the treatment of municipal or residual
waters or natural waters. Its application in the treatment of effluents with
phenols, nitro aromatic, ether aliphatic compounds and textile waters is quite
restricted because of the high toxicity inherent in these wastes, the need to
adjust the pH to an adequate value and add food and oxygen in adequate
quantities for the transforming microorganisms, as the viability of the
process depends fundamentally on the health and activity of the latter. There
are two kinds of processes in the biological treatment of biological
compounds: aerobic and anaerobic (Eckenfelder et al. 1989). Aerobic
processes are used more because of their efficiency and operational
simplicity (Ruiz et al., 1992), (Urano et al., 1986), (Kameya et al., 1995).
The results showed that it could be a good solution in the treatment of
industrial wastewater (Pala and Tokat, 2001).

I.1.8 Chemical oxidation

Oxidation, by definition, is a process by which electrons are transferred


from one substance to another. This leads to a potential expressed in volts
referred to a normalized hydrogen electrode. From this, oxidation potentials

8
Introduction

of the different compounds are obtained. Figure 5 shows the potentials of the
most commonly used oxidizers (Munter et al., 2001).

Figure 5. Oxidation power of selected oxidizing species.


Chemical oxidation appears to be one of the solutions able to comply
with the legislation with respect to discharge in a determined receptor
medium. It can also be considered as an economically viable preliminary
stage to secondary treatment of biological oxidation for the destruction of
non-biodegradable compounds which inhibit the process.
The optimization of the process (Akata and Gurol, 1992) arises in those
conditions in which non-biodegradable material is eliminated, but with a
minimum amount of oxidizer. That is to say, carrying out the oxidation to
cause the formation of biodegradable compounds and not those of CO2 and
H2O. It can be said to be an appropriate technique for small loads of
pollutants; load meaning the concentration of the pollutant multiplied by the
volume of flow of the effluent to be treated. This would otherwise become
an expensive technique, because of its large oxidizer consumption, and it
would have fewer possibilities in relation to other more appropriate
techniques for greater loads, as could be the selective absorption of

9
Chapter I

pollutants when the concentration of the pollutant is high, or biological


oxidation for low concentrations.
In addition to the polluting load, for chemical oxidation to be
economically profitable, the concentration of the polluting load in the
effluent has to be taken into account. This operation is easier to apply in the
destruction of compounds like phenol, nitrobenzene, some colorants and
their derivatives for concentrations between 100 and 500 mg/l. In the case of
higher concentrations, other operations come into play such as selective
absorption or incineration, in those cases where recuperation is not desired.
For lower concentrations, techniques such as absorption and biological
oxidation are advisable.
In general it can be said that chemical oxidation shows good prospects for
use in the elimination of non-biodegradable compounds in the following
cases:
1. For the treatment of high concentrations of the compound to
be eliminated, without the interference of other possible compounds.
For example, when incineration is not a viable alternative because
the volume of flow of the effluent is great. Optimization is obtained
because the reactant is consumed in attacking the desired compound.
The existence of other compounds, which can oxidize, leads to a
high level of consumption of the reactant.
2. As a pretreatment of currents, to reduce toxicity by avoiding
causing problems of inhibition in the biomass when being
introduced in a biological treatment (activated sludge). Intermediate
levels of oxidation are aimed at, with a reduced consumption of
oxidizer, so that the effluent is ready to be biologically treated.
3. As a final treatment for the adjustment of the effluent for the
desired discharging conditions.
A reference parameter when using chemical oxidation as a treatment
process is the COD (Figure 6).

10
Introduction

Figure 6. Suitability of water treatment technologies according to COD


contents (Andreozzi et al., 1999).
Only waters with relatively small COD contents (≤ 5 g/l) can be suitably
treated by means of these processes since higher COD contents would
require the consumption of excessively large amounts of expensive
reactants. In those cases, it would be more convenient to use wet oxidation
or incineration: waste water with COD higher than 20 g/l should undergo
autothermic wet oxidation (Mishra et al., 1995).
Chemical oxidation processes can be divided into two classes:
ƒ Classical Chemical Treatments.
ƒ Advanced Oxidation Processes (AOPs).

I.1.8.1 Classical Chemical Treatments


Classical chemical treatments generally consist of the addition of an
oxidizing agent to the water containing the contaminant to be oxidized.
Among the most widely used are (Chamarro et al. 1996):
ƒ Chlorine: This is a good chemical oxidizer for water
purification because it destroys microorganisms. It is a strong, cheap
oxidant, it is very simple to feed into the system and it is well
known. Its main disadvantages are its low selectivity, the high
amounts of chlorine required and that it usually produces
carcinogenic organochloride by-products.
ƒ Potassium permanganate: This has been extensively used in
the treatment of water for decades. It can be introduced into the
system as a solid or as a solution prepared on site. This oxidant is
strong but expensive and it works properly in a wide pH range. One
of the disadvantages of the use of potassium permanganate as an

11
Chapter I

oxidizer is the formation of magnesium dioxide throughout


oxidation, which precipitates and has to be eliminated afterwards by
clarifying or filtration, both of which mean extra costs.
ƒ Oxygen: The reaction of organic compounds with oxygen does
not take place in normal temperature and pressure conditions. The
values of temperature and pressure needed are high to increase the
oxidizing character of the oxygen in the reaction medium and to
assure the liquid state of the effluent. It is a mild oxidant that
requires large investments in installations. However, its low
operating costs make the process attractive.
ƒ Hydrogen peroxide: This is a multipurpose oxidant for many
systems. It can be applied directly or with a catalyst. The catalyst
normally used is ferrous sulphate (the so-called Fenton process,
which will be presented below). Other iron salts can be used as well.
Other metals can also be used as catalyst, for example, Al3+, Cu2+. Its
basic advantages are:
1. It is one of the cheapest oxidizers that is normally
used in residual waters.
2. It has high oxidizing power.
3. It is easy to handle.
4. It is water-soluble.
5. It does not produce toxins or colour in by-products.
It can also be used in the presence of ultraviolet radiation and oxidation is
based on the generation of hydroxyl radicals which will be considered an
advanced oxidation process.
An option to the addition of hydrogen peroxide to the reaction medium is
its production on site. One production possibility is by electroreduction of
the oxygen dissolved in the reaction medium. This option is not used very
often, because it is expensive and increases the complexity of the system.
ƒ Ozone: This is a strong oxidant (like hydrogen peroxide and
oxygen) that presents the advantage of not introducing “strange
ions” into the medium. Ozone is effective in many applications, like
the elimination of color, disinfection, elimination of smell and taste,
and the elimination of magnesium and organic compounds. In
standard conditions of temperature and pressure it has a low
solubility in water and is unstable (Whitby, 1989). It has an average
life of a few minutes. Therefore, to have the necessary quantity of
ozone in the reaction medium a greater quantity has to be used.
Among the most common oxidizing agents, it is only surpassed in
oxidant power by fluorine and hydroxyl radicals. Although included
among classical chemical treatments, the ozonation of dissolved
compounds in water can also constitute an AOP by itself as hydroxyl
radicals are generated from the decomposition of ozone, which is
catalyzed by the hydroxyl ion or initiated by the presence of traces

12
Introduction

of other substances, such as transition metal cations. As the pH


increases, so does the rate of decomposition of the ozone in water.
The major disadvantage of this oxidizer is that it has to be produced
on site and needs installation in an ozone production system in the
place of use. Therefore, the cost of this oxidizer is extremely high,
and this must be kept in mind when deciding on the most
appropriate oxidizer for a given system. In addition, as it is a gas, a
recuperation system has to be foreseen and that will make the
obtaining system even more expensive (Benitez et al., 1997).
Ozonation is used in many drinking water plants as a tertiary
treatment and also for the oxidation of organic pollutants of
industrial (paper mill industry) or agriculture (water polluted by
pesticides) effluents. Extensive research has been carried out to
investigate the kinetics of the ozonation reaction of various organic
and inorganic compounds such as carboxylic acids, phenols, amino
acids, organometallic compounds, etc. In the case of phenol, some
studies have been done in order to establish a kinetic model to
predict the magnitude of the gas-liquid reaction between ozone and
phenol. Contreras and co-workers (Contreras et al., 2001) studied
the elimination of nitrobenzene from aqueous solutions by means of
ozonation and enhanced ozonation. With regard to textile
wastewaters ozonation has been found to be very efficient for the
decolorization of textile wastewaters (Balcioglu et al., 1999),
(Ciardelli et al., 2001), (Sevimli et al., 2002). Ozone treatment may
be enhanced by the addition of hydrogen peroxide.

I.1.8.2 Advanced Oxidation Processes (AOPs)


AOPs were defined by (Glaze et al., 1987) as near ambient temperature
and pressure water treatment processes which involve the generation of
highly reactive radicals (especially hydroxyl radicals) in sufficient quantity
to effect water purification. These treatment processes are considered as very
promising methods for the remediation of contaminated ground waters,
surface waters, and wastewaters containing non-biodegradable organic
pollutants. Hydroxyl radicals are extraordinarily reactive species that attack
most organic molecules. The kinetics of reaction are generally first order
with respect to the concentration of hydroxyl radicals and to the
concentration of the species to be oxidized.
Hydroxyl radicals are also characterized by a low selectivity of attack, an
attractive feature for an oxidant to be used in wastewater treatment. Several
different organic compounds are susceptible to removal or degradation by
means of hydroxyl radicals, as shown in Figure 7. Nevertheless, some of the
simplest organic compounds, such as acetic, maleic and oxalic acids, acetone

13
Chapter I

or simple chloride derivatives such as chloroform or tetrachloroethane,


cannot be attacked by OH• radicals (Bigda, 1995). Depending upon the
nature of the organic species, two types of initial attacks are possible: the
hydroxyl radical can abstract a hydrogen atom to form water, as with alkanes
or alcohols, or it can be added to the contaminant, as is the case for olefins or
aromatic compounds.

Figure 7. Oxidizable compounds by hydroxyl radicals (Bigda, 1995).


The attack by hydroxyl radical, in the presence of oxygen, initiates a
complex cascade of oxidative reactions leading to mineralization. As a rule
of thumb, the rate of destruction of a contaminant is approximately
proportional to the rate constants for the contaminant with the hydroxyl
radical.
The versatility of AOPs is also enhanced by the fact that they offer
different ways of HO• radicals production, thus allowing a better compliance
with the specific treatment requirements. It has to be taken into account,
though, that a suitable application of AOPs to wastewater treatment makes
use of expensive reactants such as hydrogen peroxide and/or ozone.
The most important advanced oxidation treatments based on the use of
H2O2 are Fenton and photo-Fenton process.

14
Introduction

I.2 Fenton and photo-Fenton reaction

The Fenton reaction was discovered by (Fenton, 1894). Forty years later
the (Haber-Weiss, 1934) mechanism was postulated, which revealed that the
effective oxidative agent in the Fenton reaction was the hydroxyl radical.
The Fenton reaction can be outlined as follows (Figure 8):

Figure 8. Mechanism of Fenton reaction.


where M is a transition metal such as Fe or Cu.
In the absence of light and complexing ligands other than water, the most
accepted mechanism of H2O2 decomposition in acid homogeneous aqueous
solution, which involves the formation of hydroxyperoxyl (HO2•/O2-) and
hydroxyl radicals HO• (De Laat and Gallard, 1999), (Gallard and De Laat,
2000).
The HO• radical mentioned above, once in solution attacks almost every
organic compound.
Fenton reaction rates are strongly increased by irradiation with
UV/visible light (Ruppert et al., 1993), (Pignatello and Sun, 1993). During
the reaction, Fe3+ ions are accumulated in the system and after Fe2+ ions are
consumed, the reaction practically stops. Photochemical regeneration of
ferrous ions (Fe2+) by photoreduction of ferric ions (Fe3+) is the proposed
mechanism. The newly generated ferrous ions react with H2O2 generating a
second HO• radical and ferric ion, and the cycle continues (Figure 9):

Figure 9. Mechanism of photo-Fenton reaction.


Fenton and photo-Fenton reaction depend not only on H2O2 concentration
and iron added, but also on the operating pH value.

I.2.1 Basic Principles

I.2.1.1 The Fenton Process


The oxidative decomposition and transformation of organic substrates by
H2O2/Fe2+ (known as Fenton’s reagent) has been known of nearly a century
(1894). This method has the advantage that hydrogen peroxide, used as
oxidant, is cheaper than other oxidants and it also has the advantage of using

15
Chapter I

iron as catalyst. Iron is the second most abundant metal and the fourth most
abundant element on earth. In water it is present as ferric or ferrous ions,
which form complexes with water and hydroxyl ions depending on pH and
the temperature. Figure 10, shows the percentage of Fe2+ and the species that
appear together with it, in relation to the pH at 25 °C and where it is possible
to see that up to a pH level around 8, Fe2+ exists in solution.

Figure 10. Proportion of Fe2+ and the species in equilibrium with it at 25°C.
From this, it can be concluded that Fe2+ in the Fenton system will be in
this form and in solution. Figure 11 shows the concentration of Fe3+ in
solution in relation to the pH at 25°C. This representation has been carried
out for a pH of between 2 and 3.2 because this is the solubility limit. As can
be observed, the solubility of Fe3+ is very high for a pH lower than 2 and too
small for a pH higher than 3.2. Therefore, in Fenton conditions Fe3+ will be
in solution if pH is maintained < 3.2.

16
Introduction

Figure 11. Concentration of Fe3+ in solution in relation to the pH at 25°C.

Figure 12 shows the proportion of Fe3+ species that are in equilibrium in


relation to the pH (Safarzadeh-Amiri, 1996).

Figure 12. Proportion of Fe3+ and the existing species in equilibrium with it
at 25°C

From this figure, the low solubility of Fe3+ and all its species can be seen
at pH 3.
At pH 3 the solubility of Fe3+ is around 4 mg/l. According to (Eisenhauer,
1964), in spite of the low solubility of Fe3+ in presence of phenol in the
reaction medium, ferric hydroxide does not precipitate throughout oxidation
because it is transformed into Fe2+ due to the reaction of Fe3+ with some
products of phenol oxidation. The commonly mentioned disadvantage of the

17
Chapter I

Fenton method is the necessity to work at low pH (normally below 4),


because at higher pH ferric ions would begin to precipitate as hydroxide. In
addition, by this process the maximum mineralization reached is around 40-
60 %.
Although the Fenton reagent has been known of more than a century and
shown to be a powerful oxidant, the mechanism of the Fenton reaction is still
under intense and controversial discussion. Generation of HO• radicals by
the dark reaction of H2O2 with ferrous salt has been the subject of numerous
studies during the last decade (Chen and Pignatello, 1997), (Hislop and
Bolton, 1999). The oxidizing species generated in the Fenton reaction have
been discussed by many researchers but are still controversial (Macfaul,
1998), (Goldstein, 1999), (Kremer, 1999). The recognition of the HO• radical
as the active intermediate is not yet universal and even doubts as to its very
existence in the system have been raised, (Bossmann et al., 1998) outlined
clearly that recent thermodynamic calculations have demonstrated that the
outher-sphere electron-transfer reaction between Fe2+ and H2O2, as it is
rationalized by the classic mechanism proposed by Haber and Weiss, cannot
take place, because the formation of H2O2 by intermediates is not favored.
In contrast, the formation of a hydrated Fe2+-H2O2 complex is
thermodynamically favored. However, in the main studies of the Fenton
reagent, it is generally considered that the reaction between H2O2 and Fe2+ in
an acidic aqueous medium (pH ≤ 3) produces HO• radicals and can involve
the steps presented below (Figure 13).

Figure 13. The Fenton Reaction: scheme of mechanism.


The hypothesis of (Haber and Weiss, 1934), that the Fenton reaction
involves the formation of ΗΟ• radicals has been proved by many techniques,
including EPR spectroscopy. Although a considerable number of
researchers, by using the EPR spintrapping technique, have found evidence

18
Introduction

for the formation of ΗΟ• radicals from the Fenton reagent (Rosen et al.,
2000), it has also been reported by others that this species is not the only
oxidizing intermediate, but also some type of high-valent iron-oxo
intermediates are present (Kremer, 1999), (Bossmann et al., 1998). Using
EPR spin-trapping, three types of oxidizing species (free HO•, bound HO•,
and high-valence iron species, which is probably a ferryl ion, (FeIV) were
detected by (Yamazaki and Piette, 1991). In the present work, the principal
oxidant is assumed to be ΗΟ• radical, but others such as iron-oxo species
cannot be ruled out.

I.2.1.2 The photo-Fenton process


Basic chemistry, as well as applications of Fe2+/H2O2 and Fe3+/H2O2
system for hazardous waste treatment are used. Ferrous ion combined with
hydrogen peroxide (Fenton’s reagent) reacts stoichiometrically to give HO•
according to Figure 14:

Figure 14. Reaction of ferrous ion combined with hydrogen peroxide.


In the dark, the reaction is retarded after complete conversion of Fe2+ to
3+
Fe . Nowadays, it is known that the oxidizing power of the Fenton system
can be greatly enhanced by irradiation with UV or UV-visible light.This
effectiveness has been proven with the total mineralization of many organic
compounds in aqueous solution. The reason for the positive effect of
irradiation on the degradation rate include the photo-reduction of Fe3+ to Fe2+
ions, which produce new HO• radicals with H2O2 (Figure 15) according to
the following mechanism:

Figure 15. The photo-Fenton Reaction: scheme of mechanism.


There are more equations (as shown in chapter 1 and 3) involved in the
mechanism of hydroxyl radical generation, but those cited are the most
significant. The main compounds absorbing light in the Fenton system are
ferric ion complexes, e.g. [Fe3+ (OH)-]2+ and [Fe3+ (RCO2)-]2+ , which
produce additional Fe+2 by following (Figure 16) photo-induced, ligand-to-
metal charge-transfer reactions (Sagawe, 2001).

19
Chapter I

Figure 16. Photo-induced reactions.


Additionally, the first equation yields HO• radicals, while the second
equation results in a reduction of the total organic carbon (TOC) content of
the system due to the decarboxylation of organic acid intermediates. It is
very important to note that both reactions form the ferrous ions required for
the Fenton reaction. The overall degradation rate of organic compounds is
considerably increased in the photo-Fenton process, even at lower
concentration of iron salts present in the system.

I.3 Aim of the work

Homogeneous photo-Fenton has been widely investigated as an


innovative for environmental applications such as detoxification processes in
water. In contrast, very few studies have been conducted concerning
heterogeneous photo-Fenton. Concerning this last aspect, the study has been
devoted to the selection of solid catalyst, able to substitute the Fenton
homogeneous catalyst. The kind and shape of solid catalysts and photo-
Fenton operative conditions process have been investigated on model
wastewaters.

20
II State of the art

II.1 The homogeneous Fenton reaction

The homogeneous Fenton reaction is already in use in industrial


wastewater purification processes (Centi et al., 2000).
For example, a study was made of catalytic wet hydrogen peroxide
oxidation of propionic acid with a homogeneous iron catalyst (Fe(NO3)3) at
room temperature and 70 °C as a function of the time of reaction. The
H2O2/substrate ratio was 1.5 times the stoichiometric value necessary to
completely oxidize all the propionic acid present in solution to CO2.
Propionic acid was used as a model reactant, because it gives rise to
acetic and formic acids as primary intermediates. These two carboxylic acids
are the common products of the oxidation of several organic molecules
(Delanghe et al., 1991) and acetic acid is one of the most ‘recalcitrant’
molecules (Gallezot et al., 1996), (De Leitenburg et al., 2004). As a probe
molecule, propionic acid can thus give direct information on reactivity in the
attack on the carbon chain as well as information on the reactivity of its
primary products of oxidation (formic and acetic acids).
Maximum activity around a pH of 4 was observed in propionic acid
conversion. Upon decreasing or increasing the initial pH of the solution
below or above 4, the rate of hydrogen peroxide decomposition increased
due to partial transformation of iron to other species catalysing this reaction.
A number of studies on the degradation of Nitrobenzene in aerated
aqueous solutions by the Fenton reagent have been reported (Lipczynska-
Kochany, 1991). Nitrobenzene is one of the most representative
nitroaromatic compounds, which is present in several wastewaters. Phenol is
also the most typical and common model compounds used in the application
of different advanced oxidation processes as treatment methods (Benitez et
al., 2000), (Vicente et al., 2002). Some organic catalyst supports have been
studied, such as styrene divinyl benzene (SDB) co-polymer as support for Pt
catalyst in catalytic oxidative nitrate removal from wastewater (Huang et al.,
2001).
Chapter II

II.2 The heterogeneous Fenton reaction

Several studies have been published concerning supporting a Fenton


catalyst to various carriers, such as brick grain (Chou et al., 2001), MgO
(Pak et al., 1999), SiO2 (Huling et al., 2000), and zeolite (Centi et al., 2000),
(Fajerwerg and Debellefontaine, 1996), (Fajerwerg, et al., 1997), (Larachi et
al., 1998), (Centi et al., 2001), (Neamtu et al., 2004). Also copper or iron
containing pillared clays were used as Fenton catalysts (Abdellaoui et al.,
1999).

II.2.1 The heterogeneous Fenton reaction with zeolite

Zeolite shows a possible role in enhancing the rate of reaction by the


local change of the concentration of the reactants inside zeolite
microcavities. A zeolite named as FeZSM-5 is the most active heterogeneous
Fenton-type catalyst. The studies of (Centi et al., 2000) on FeZSM-5 in wet
hydrogen peroxide oxidation of diluted propionic acid solutions at
atmospheric pressure in a batch reactor, shows that the solid catalyst has a
higher rate of conversion (the rate of reaction is higher for the homogeneous
catalyst by a factor of about 3–5) of the substrate as well as a lower
sensitivity with respect to pH than Fe3+ ions in solution at the same reaction
conditions (temperature, amount of H2O2, amount of iron). However, the
solid catalyst has a major drawback in its higher rate of hydrogen peroxide
decomposition to water and oxygen.
Although it was demonstrated that the activity of the solid catalyst is not
related to leached iron ions, slight leaching of iron was found to be present,
especially at the higher reaction temperatures. This could cause deactivation
with prolonged use.
Calcination is probably necessary to burn the organic species which
remain trapped in the zeolite which delay the start of the activity of the
zeolite during consecutive catalytic experiments.
The use of FeZSM5 as a heterogeneous catalyst under mild conditions
(T=90°C, H2O2 stoichiometric ratio, 1.5, atmospheric pressure in a batch
reactor) allows significant TOC removal and total elimination of phenol at
pH=5 (Fajerwerg et al., 1997).
FeZSM-5 is also active in oxidation of diethylnitrophenil phosphate,
which is hardly detoxified by other methods (Kuznetsova et al., 2004).
Catalytic wet peroxide oxidation on Fe-exchanged Y zeolite of Procion
Marine H-EXL and of dye-bath effluents containing this dye can be a
suitable pre-treatment method for complete decolorization of effluents from
textile dyeing and finishing processes, once the optimum operating
conditions are established. Catalytic oxidation by hydrogen peroxide of an

22
State of the art

aqueous solution of Procion Marine H-EXL on FeY leads to TOC and COD
removals when the system operates at pH = 5, T = 50 °C, 1 g/l catalyst and
20 mmol/l H2O2. The catalytic oxidation of synthetic textile wastewater
assures better color and COD removals (>90%) after an operational time of
60 min (Neamtu et al., 2004).

II.2.2 The heterogeneous Fenton reaction with perovskite

Additionally, perovskite-type oxides have attracted great interest for the


development of environment-friendly catalytic materials. They have been
used in processes such as catalytic combustion of automobile control
emissions (Seiyama et al., 1992) and the catalytic destruction of chlorinated
compounds (Sinquin et al., 2001).
Catalytic wet peroxide oxidation of phenolic aqueous solution over
LaTi1−xCuxO3 perovskites has shown complete removal of aromatic
compounds and high TOC reduction (ca. 90%) under mild reaction
conditions (temperature of 80 ◦C and initial peroxide concentration lower
than stoichiometric) (Sotelo et al., 2004).

II.3 UV/oxidation processes

The UV/oxidizer system involves direct excitation of the substrate due to


radiation with the subsequent oxidation reaction. Even so, there may be
synergism between the oxidizer and the ultraviolet radiation, which causes
the global effect to be different from the additive effect. UV/oxidation
processes generally involve generation of OH. radicals through UV
photolysis of H2O2 or photo-Fenton.

II.3.1 Photolysis of hydrogen peroxide

The most direct method for the generation of hydroxyl radicals is through
the cleavage of H2O2. Photolysis of H2O2 yields hydroxyl radicals by a direct
process with a yield of two radicals formed per photon absorbed by 254 nm
(Baxendale and Willson, 1957). The scheme of the radical reactions is
(eqs.1-14):
Initiation (eq. 1):

H2O2 +hv→2OH. (1)

23
Chapter II

Hydroxyl-radical propagation and termination steps (eqs. 2-7):

OH.+H2O2→O2-+H2O+H+ (2)

OH..+HO2-→O2-+OH-+H+ (3)

OH.+HCO3-→CO3-.+H2O (4)

OH.+CO32-→CO3-.+OH- (5)

OH.+O2-→ OH-+O2 (6)

OH.+organic compound→ products (7)

Superoxide and carbonate-radical propagation and termination steps (eqs.


8-14):

O2-+H2O2→OH.+OH-+O2 (8)

O2-+HCO3-→HO2-+CO3-. (9)

O2-+CO3-.→O2+CO3-2. (10)

2 O2-+2H2O→H2O2+2OH-+O2 (11)

CO3-.+H2O2→HCO3-+O2-+H+ (12)

CO3-.+HO2-→HCO3-+O2- (13)

CO3-. + organic compound→ ? (14)

Low-pressure mercury vapor lamps with a 254 nm peak emission are the
most common UV source used in the UV/H2O2 system. The maximum
absorbance of H2O2 occurs at about 220 nm. If low-pressure lamps are used,
a high concentration of H2O2 is needed to generate sufficient hydroxyl
radicals. However, high concentration of H2O2 scavenges the radicals,
making the process less effective (eqs.15-17):
OH.+H2O2→HO2.+H2O (15)

HO2.+H2O2→OH.+H2O2+O2 (16)

HO2.+ HO2.→ H2O2+O2 (17)

24
State of the art

II.3.2 The homogeneous photo-Fenton reaction

A number of studies on the degradation of 4-chlorophenol (Ghaly et al.,


2001), nitrophenols (Kiwi et al., 1994), (Trapido and Kallas, 2000) and
phenols by photo-Fenton have been reported (Kavitha et al., 2004).
Phenol is also the most typical and common model compound used in the
application of different advanced oxidation processes as a treatment method
(Benitez et al., 2000), (Vicente et al., 2002).
For example, in photo-Fenton processes (solar/UV light), complete
degradation of phenol was observed at 50% of ferrous ion catalyst as
compared with the Fenton process suggesting the importance of solar/UV
light in the process of mineralisation. In the Fenton process, carboxylic acids
such as acetic acid and oxalic acid were formed as end products during the
degradation of phenol while in photo-Fenton processes, both these ions were
identified during the early stages of phenol degradation and were oxidized
almost completely at 120min of the reaction time (Kavitha et al., 2004).
An improvement of photoassisted Fenton processes is the UV-
vis/ferrioxalate/H2O2 system, which has recently been demonstrated to be
more efficient than photo-Fenton for the abatement of organic pollutants.
The use of ferrioxlate in the photo-Fenton reaction for the
degradation of organic pollutants was reported to be very effective in
the degradation of 2-propanol.
The ferrioxalate complex [Fe(C2O4)3]3- is higly photoreactive and the
reduction of Fe(III) to Fe (II) can occur at a wavelength further into the
visible spectrum (about 550 nm) (Hislop and Bolton, 1999).

II.3.3 The heterogeneous photo-Fenton reaction

Many efforts have been made to develop heterogeneous photo-Fenton


catalysts for wastewater treatment (Fernandez et al., 1998); (Li Puma and
Yue, 2000); (Bossmann et al., 2001), (Feng et al., 2003). In general, two
types of heterogeneous photo-Fenton catalysts are used in the degradation of
organic compounds. One is the suspended catalyst and the other is the fixed
bed catalyst. Compared with the suspended catalyst, the biggest advantage of
a fixed bed catalyst lies in the fact that after wastewater treatment, separation
of catalyst from reaction solution is not needed, and the catalyst can be used
for a batch photo-reactor as well as a continuous photo-reactor even though
the fixed bed catalyst normally exhibits a decreased photo-catalytic activity
due to the decrease in specific surface area.
For example, (Bossmann et al., 2001) prepared Fe(III)-doped zeolite Y
catalyst through a simple ion exchange reaction (Fe3+ vs. Na+) and used it as
a suspended photo-Fenton catalyst for the degradation of polyvinyl alcohol.

25
Chapter II

However, this catalyst exhibited very poor catalytic activity because after
120 min reaction, dissolved organic carbon remains at a high level.
Recently, laponite and bentonite clay-based Fe nanocomposite (Fe-Lap-
RD and Fe-B) have been developed as suspended photo-Fenton catalysts for
the degradation of organic dyes including azo dye Orange II and reactive dye
HE-3B in the presence of UVC light and H2O2. Under optimal conditions
(pH=3.0, H2O2 (C=10mM), and lamp of 8W-UVC), 100% discoloration and
50–60% TOC removal of 0.2mM Orange II can be achieved in 90 and 120
min, respectively (Feng et al., 2005).
While (Maletzky et al., 1999), (Sabhi and Kiwi, 2001) prepared iron ions
immobilised on nafion perfluorinated to degrade chlorophenols. 42 % TOC
removal of 1.4 mM of 4-chlorophenol can be achieved in 300 min.
This process can take place in neutral pH solutions with close to equal
efficiency as in acidic solutions, which removes the need for costly pH
adjustments when subsequent biological degradation is to be used. The
membrane could be reused through many cycles, without leaching out of a
significant amount of Fe(III) ions from the membrane, which would cause
loss of efficiency (Sabhi and Kiwi, 2001).
In a recent review, attention has been called to the fact that carbon
nanotubes (CNT) are attractive and competitive catalyst supports when
compared to activated carbon due to the combination of their electronic,
adsorption, mechanical and thermal properties (Serp et al., 2003). Some
recent works have concentrated on the preparation of new hybrid materials
CNT-TiO2. A sol-gel method has been used to prepare a composite material
made of CNT within a TiO2 matrix (Vincent et al., 2002). Multi-walled
carbon nanotube-based titania composite material has also been prepared by
an impregnation method (Hernadi et al., 2003), which provided a
homogeneous inorganic cover layer on the surface of purified MWCNT.
Rutile TiO2 has been immobilized on the sidewall of MWCNT by a simple
one-step scheme, which produces three distinct morphologies of hybrid
MWCNT at different reaction temperatures (Huang et al., 2003). Coating
MWCNT surface with TiO2 has been performed by a sol-gel method using
different alkoxides and by hydrothermal hydrolysis of TiOSO4, which can
lead to different morphologies (Jitianu et al., 2004). Recently, composite
nano-fibers made of polyacrilonitrile (PAN) matrix, into which both
MWCNT and titanium dioxide particles were incorporated by
electrospinning, were introduced by (Kedem et al., 2005). It was found that
the coupling between the photocatalyst and the CNT affected the self
photodegradation of the fibers as well as the photodegradation of various
contaminants such as CCl4 (Kedem, 2005). Hence, composites containing
carbon nanotubes are believed to provide many applications and exhibit
cooperative or synergetic effects between the metal oxides and carbon
phases.

26
State of the art

Early findings regard the application of photocatalytic advanced


oxidation with hydrogen peroxide to the purification treatment for winery
wastewaters (Navarro et al., 2005). Wine and grape wastewaters are more
difficult to treat than other wastewaters from food processing plants.
Wineries generate effluents that are characterized by high organic matter
concentration, acidity, unpleasant odours and noticeable seasonal variability,
being discharged only during grape harvest and racking periods (3–4 months
per year) (Brucculeri et al. 2005).

27
III Experimental methods

III.1 Catalyst characterization

To characterize the samples studied in this work the following techniques


were used:
• Inductively coupled plasma-mass spectrometry (ICP-MS);
• Thermal analysis (TG-MS);
• N2 adsorption at -196 °C to obtain specific surface area and
porosity characteristics:
• Micro Raman spectroscopy;
• SEM analysis;
• Near infrared, ultraviolet and visible diffuse reflectance
spectroscopy (NIR-UV-VIS DRS).

III.1.1 ICP-MS

Inductively Coupled Plasma Mass Spectrometry (ICP-MS) is extensively


used to detect and quantify the presence of the majority of the elements in
the periodic table and is a very powerful tool for trace (ppb-ppm) and ultra-
trace (ppq-ppb) elemental analysis. In ICP-MS, the plasma is formed from
Argon gas and reaches very high temperatures of up to approximately 7000
K. The plasma is used to atomize and ionize the elements in a sample. The
sample to be analysed is introduced into the plasma as a fine aerosol. As the
sample aerosol passes through the plasma, it collides with free electrons,
argon cations and neutral Argon atoms. The result is that any molecules
initially present in the aerosol are quickly and completely broken down into
charged atoms. The resulting ions are then passed through a series of
apertures (cones) into the high vacuum analyzer. The isotopes of the
elements are identified by their mass-to-charge ratio (m/z) and the intensity
of a specific peak in the mass spectrum is proportional to the amount of that
isotope (element) in the original sample. An ICP-MS Agilent 7500 E
Chapter III

instrument was used for the analysis of Fe. Alternatively, it was used for the
analysis of Mn, Co, Cu, Fe and Ni an ICP-AES Varian “Liberty II” by
courtesy of SSIP (Napoli).

III.1.2 Thermal analysis (TG-MS)

The performances of samples as a function of temperature were


determined by air flow thermal analysis (TG-MS). The apparatus used were
a TGAQ500 (Figure 17) thermogravimetric analyzer (TA Instruments) and a
SDTQ600 (Figure 18) simultaneous DSC/TGA (TA Instruments). Both
analyzers can be coupled to a Pfieffer Vacuum Benchtop Thermostar mass
spectrometer (MS) (Figure 19).

Figure 17. TGAQ500 Thermogravimetric Analyzer.

Figure 18. SDTQ600 Simultaneous DSC/TGA.

30
Experimental methods

Figure 19. Pfieffer Vacuum Benchtop Thermostar mass spectrometer.

TGAQ500 measures weight changes in a material as a function of


temperature. The system works in a temperature range of 20-1000 °C, and
weight variation resolution is 0.1mg . The sample, loaded in a crucible made
of platinum and connected to the balance arm by a small hook, is
progressively heated in the oven. A thermocouple controls the oven
temperature and a second thermocouple reads the sample temperature.
Sample pan loading and furnace movement are totally automated and there is
a touch screen data display to change operating parameters. Typically,
measurements are carried out with 20 mg of the sample in chromatographic
air flow (60 Ncc/min) with a heating rate of 10 °C/min in the temperature
range of 20- 800 °C.
The results are displayed as TG curves showing the mass variations as
functions of temperature or time, and DTG curves showing the conversion
rate (mass loss percentage per unit time) as functions of temperature or time.
Figure 20 contains the typical trends of the TG and DTG curves.

31
Chapter III

100 3

98

2
96

DTG (%/min)
94
TG (%)

1
92

90
0

88

86 -1
0 100 200 300 400 500 600
Temperature (°C)

Figure 20. TG and DTG curves.


SDTQ600 provides simultaneous measurement of weight change (TGA)
and heat flow (DSC) on the same sample from ambient to 1500 °C. It
features a proven horizontal dual beam design with automatic beam growth
compensation, and the ability to analyze two TGA samples simultaneously.
DSC heat flow data is dynamically normalized using the instantaneous
sample weight at any given temperature. The sample is loaded into a crucible
made of alumina and heated in the horizontal oven. There are two
thermocouples to control the oven temperature and the sample temperature.
Measurements are carried out with about 30 mg of sample in
chromatographic air flow (100 Ncc/min) with a heating rate of 10 °C/min in
the temperature range of 20- 800 °C.
The Pfieffer Vacuum Benchtop Thermostar mass spectrometer can
measure the gas evolved from thermal analyzers up to 300 AMU. The
evolved gases are introduced into a heated quartz capillary, which is
extremely fine, in order to produce the necessary high vacuum when the
evolved gases enter the mass spectrometer. The heated capillary is necessary
in order to prevent condensation of the hot gases on cold surfaces. The
analysis of gases is performed by a very highly sensitive quadrupole mass
detector. The necessary high vacuum is obtained through 2 stages of vacuum
pumps that are integrated into a compact housing. The first stage is a rotary
pump; second stage is a turbo molecular pump.
Both systems, the Mass Spectrometer and Thermal Balance, are
connected to a common PC for data acquisition.

32
Experimental methods

III.1.3 N2 adsorption measurements

In order to study the porosity of catalyst powders, N2 adsorption


measurement were carried out at -196 °C with a Costech Sorptometer 1040
(Figure 21).
The measurement was performed by continuous-flow method after
sample pre-treatment at 150 °C for 2 h in He flow, in order to measure total
specific surface area (via single and multi-point methods) and micropore
volume (via micropore method).

Figure 21. Costech Sorptometer 1040.

III.1.4 The micro Raman spectroscopy

Raman spectroscopy is a technique for the identification and


quantification of the chemical components of specimens.
When light is scattered by any form of matter, the energies of the
majority of the photons are unchanged by the process, which can be elastic
or Rayleigh scattering. However, about one in one million photons or less,
lose or gain energy that corresponds to the vibrational frequencies of the
scattering molecules. This can be observed as additional peaks in the
scattered light spectrum. The process is known as Raman scattering and the
spectral peaks with lower and higher energy than the incident light are
known as Stokes and anti-Stokes peaks respectively.

33
Chapter III

Laser Raman spectra of powder samples were obtained with a Dispersive


MicroRaman (Invia, Renishaw) (Figure 22), equipped with a 514.5 nm
diode-laser, in the 200-900 cm-1 Raman shift range.

Figure 22. Dispersive MicroRaman (Invia, Renishaw).

III.1.5 SEM analysis

The scanning electron microscope (SEM) is a type of electron


microscope capable of producing high resolution images of a sample surface.
Due to the manner in which the image is created, SEM images have a
characteristic three-dimensional appearance and are useful for judging the
surface structure of the sample.
In a typical SEM, electrons are thermionically emitted from a tungsten or
lanthanum hexaboride cathode and are accelerated towards an anode;
alternatively electrons can be emitted via field emission (FE). Tungsten is
used because it has the highest melting point and lowest vapour pressure of
all metals, thereby allowing it to be heated for electron emission. The
electron beam, which typically has energy ranging from a few hundred eV to
50 keV, is focused by one or two condenser lenses into a beam with a very
fine focal spot sized 1 nm to 5 nm. The beam passes through pairs of
scanning coils in the objective lens, which deflect the beam in a raster
fashion over a rectangular area of the sample surface. As the primary
electrons strike the surface they are inelastically scattered by atoms in the
sample. Through these scattering events, the primary electron beam
effectively spreads and fills a teardrop-shaped volume, known as the
interaction volume, extending from less than 100 nm to around 5 µm into the
surface. Interactions in this region lead to the subsequent emission of
electrons which are then detected to produce an image. The textural features
of supported perovskites were studied by SEM with a BS-350 machine of
the Boreskov Institute of Catalysis (Russia) (resolution limit is about 5–10
nm).

34
Experimental methods

III.1.6 NIR-UV-VIS DRS

Near infrared, ultraviolet and visible diffuse reflectance spectroscopy


(NIR-UV-VIS DRS) was carried out in the 200-1100 nm range with a
PerkinElmer lambda 35 spectrophotometer equipped with a reflection sphere
in the 200-1100 nm range.

III.1.7 XRD spectroscopy

X-Ray diffraction was performed to verify whether the ionic exchange


induced changes in the zeolite structure. Spectra of powder are analysed with
the step-scan method of 2θ =0.02, with a D8000 Bruker diffractometer.

III.2 Laboratory apparatus for catalytic Fenton oxidation

The Figure 23 is an illustration of laboratory apparatus for the experiment


set up.

35
Chapter III

Sampling needle PH electrode


pH-
Helical mixer PT 100 probe
Termo

Agita

Siringa

Bagno

Figure 23. Laboratory apparatus for catalytic Fenton oxidation.


Catalytic tests for oxidation with hydrogen peroxide were carried out in a
glass batch reactor at ambient temperature. Continuous stirring of 250 ml or
100 ml of freshly prepared aqueous solution containing an organic
compound concentration corresponding to TOC of 1000 mg/l or 500 mg/l in
contact with ambient air was performed by a helical mixer. A concentrated
solution of H2O2 was added to achieve a fixed H2O2/substrate stoichiometric
ratio. The catalysts were added both in powder form and from precursor
aqueous solutions. Temperature was monitored by a PT100 probe.
Temperature control was obtained by placing a glass batch reactor in a
thermostatic bath.
Alternatively, for tests on structured catalysts at ambient temperature, a
closed vessel batch reactor placed on an oscillating plate was employed.
The TOC of the solution was measured as function time with devoted
instrumental laboratory plant, designed, realised and optimised to the
purpose, as described in paragraph III.4 . The H2O2 concentration was
determined by H2O2/TiOSO4 complex (λ = 405 nm) UV-Vis analyses.

36
Experimental methods

III.3 Laboratory apparatus for catalytic photo-Fenton oxidation

The Figure 24 an illustration of laboratory apparatus for the experiment


set up.

8 W mercury vapor lamp emitting at 254 nm Gas out


Thermocouple Condenser
N2
H2O Out CO

Air
CO 2

CO2/N2
Analyzers
Cooler (T=O°C)
CO/N2 H2O IN
Structured catalyst
Pump
1 2

3 4

Figure 24. Laboratory apparatus for the catalytic photo-Fenton oxidation.


Catalytic tests were carried out in a properly designed sealed stainless-
steel batch photoreactor.

Figure 25. Sealed stainless-steel batch photoreactor.

37
Chapter III

Organic compound aqueous solutions containing total organic carbon


concentration (TOC) in the range 250-500 mg/l (pH 3.9) and H2O2 0.083-
0.167 mol/l were used. H2O2 concentration of 0.083 mol/l was chosen
according to the reaction (eq. 18):
CH3COOH + 4 H2O2→2 CO2+6 H2O (18)
A 8 W mercury vapor lamp double envelope in special soft glass and
quartz glass as inner material, was chosen for the emission at 254 nm (Table
1).
Table 1. Characteristic of the UV lamp utilised.
Lamp Length Diam. Lamp UV Output Average
Wattage (L,mm) (D, mm) current µW/cm2 Life (h)
(W) (A) (at 1m)
8 214 20.6 0.230 16.3 3000

The monolith catalysts were placed in the bottom of reactor in an holder,


represented in fig. Figure 26.

Figure 26. Components of the sealed stainless-steel batch photoreactor.

The Figure 27 shows the ultraviolet spectrum of the UV lamp used.

38
Experimental methods

4,5

4
Spectral irradiance, a.u.

3,5

2,5

1,5

0,5

0
240 260 280 300 320 340 360 380 400

Wave lenght, nm

Figure 27. The ultraviolet spectrum of the UV lamp used.


TOC has been evaluated as function of time by COX obtained by catalytic
combustion at T=850°C. The H2O2 concentration was determined by
H2O2/TiOSO4 complex (λ = 405 nm) UV-Vis analyses. Continuous mixing
of model wastewaters was realised by gas fine bubbling under monolith
holder (Q=250 Ncc/min). and external recirculation. Before reimmission into
the reactor, the solution was cooled by a cold trap. The volume (100 ml) of
freshly prepared aqueous solution of the carboxylic acid with TOC of 500
mg/l was added to the reactor together with the catalyst, Then a concentrated
solution of H2O2 was added to achieve a fixed H2O2/substrate stoichiometric
ratio. The TOC of the solution was measured as function time. At the reactor
outlet the gases pass through a cold trap (0°C) in order to assure water
condensation, prior to the gas analysers for measurements of CO and CO2
concentrations.
The catalytic properties of micromonolithic samples with volume 5.5- 6.5
3
cm and weight 5-6 g were tested in the photo-Fenton reaction under
atmospheric pressure at 25 °C.

III.4 Laboratory apparatus for total organic carbon analysis.

In order to determine the quantity of organically bound carbon, the


organic molecules must be broken down to single carbon units and converted
to a single molecular form that can be measured quantitatively. TOC
methods utilize heat and oxygen, ultraviolet irradiation, chemical oxidants,
or combinations of these oxidants to convert organic carbon to carbon
dioxide (CO2).

39
Chapter III

TOC has been determined by the high temperature combustion method


by means of a catalyst (Pt/Al2O3) at T=850°C, with a stream of hydrocarbon
free air to oxidize the organic carbon.
Laboratory apparatus (Figure 28) consists of mass flow controllers
(Brooks) operating on each gas; an injection system; a NDIR continuous
analyser (Hartmann & Braun Uras 10E) for measurements of CO and CO2
concentrations at the reactor outlet and a paramagnetic analyser (Hartmann
& Braun Magnos 6G) for continuous monitoring of O2 concentration.
In particular, the injection of a fixed volume of the solution (250 ml) was
realized by means of a microliter syringe (Hamilton), with a pneumatic
system at pressure P= 2 bar, in the heated line (T=170°C) before the reactor.
At the reactor outlet the gases pass through a cold trap (0°C) in order to
assure water condensation, prior to going through the gas analysers.
Finally, the signals from the analysers are acquired and processed by
personal computer.
The CO and CO2 concentration data were jointly integrated to calculate
total organic carbon. The gas flow with a rate of 250 Ncc/min and
composition of 21 % vol of O2 in N2 was feed.
Gas out
N2
Thermocouple
CO
Heater Condenser
Air
Furnace
CO 2

CO2/N2
O2

CO/N2 Analyzers

Heated line Reactor


1 2

3 4

MFC Control Unit

Figure 28. Set-up of experiment for total organic carbon analysis.

III.5 Analytical method for H2O2 determination

This method involves reacting a sample which contains residual H2O2


with titanium sulphate to produce a yellow peroxo-complex. The sample is
then analyzed by spectrophotometer at 405 nm, and the absorption compared
to a standardized curve.
This procedure is appropriate for determining residual H2O2 present in
waters and wastewaters in concentrations ranging from 1 - 10 mg/l in
undiluted samples, or higher concentrations provided appropriate dilution.
The procedure is reported below:

40
Experimental methods

1. Sample pre-treatment: filter the sample if it is cloudy and prepare


appropriate dilutions.
2. Transfer 1.0 mL sample to a 25-50 ml beaker.
3. Pipet 9.0 ml ultrapure water into the beaker and stir to mix.
4. Add 1.0 mL TiSO4 solution to the beaker and stir to mix.
5. Allow the solution to develop color for 2 minutes.
6. Spectrophotometric measurement: turn on the instrument and
allow it to warm up for 5 - 10 minutes, set the instrument
wavelength to 405 nm, insert ultrapure water blank and adjust
instrument needle to full scale (0% Absorbance), insert sample
and read Absorbance, determine H2O2 concentration by
referencing from known H2O2 concentrations.

41
IV Experimental results: Fenton
oxidation of acetic acid on FeY
zeolite

IV.1 Samples preparation

IV.1.1 The HY based catalyst

Synthetic HY with an Si/Al ratio of 11.5 (Engelhard) was used as the


parent zeolite (Figure 29).
Chapter IV

Figure 29. Y structure.


The FeY sample was prepared by ion exchange starting from the
ammonium form of HY zeolite (Si/Al = 2.6). Ion exchange was carried out
at 80 °C using a 0.01 M aqueous solution of (CH3COO2)2(Fe). The time of
ion exchange was 8 h and the amount of iron introduced into the zeolite was
6 wt.%. After drying at 120°C overnight, the samples were calcined typically
at 550 °C for 2 hours.
Table 2 contains the sample prepared, with indications of the number of
exchanges, the total time of exchanges, the form of the starting zeolites and
the concentration of the metal solutions.
Table 2. Procedure of ion exchange for samples.
Sample Number Total Starting (CH3COO2)2Fe Fe, %
of time, h cation mol/l weight
exchanges
FeY 1 8 H+ 0.01 6

44
Experimental results: Fenton oxidation of the acetic acid on FeY zeolite

IV.2 Catalysts characterisation

IV.2.1 Specific surface area and chemical analysis

Surface area and porosity were obtained by N2 adsorption at 77 K.


The microporous volume obtained by the t-plot method is 0.206 cm3/g for
HY, as shown in Table 3, and decreases for FeY.

Table 3. Microporous volume of HY and FeY.


Catalysts Nominal Fe Fe by ICP Microporous
content, wt% analysis volume cm3/g
wt,%
HY 0 - 0.206

FeY 6.0 6.1 0.154

Iron exchange leads to a small reduction in volume.

IV.2.2 X-ray diffraction spectroscopy (XRDS)

X-Ray diffraction spectra of FeY and HY catalysts are reported in Figure


30.

45
Chapter IV

FeY
HY
Intensity, a.u.

5 10 15 20 25 30 35 40
2 teta

Figure 30. X-Ray diffraction spectra of FeY and HY catalysts.


For an HY sample the diffraction peaks are in good agreement with
literature data (Treacyand, Higgins, 2001). Moreover it can be observed that
no substantial difference appears by comparing the peaks of the calcined
FeY sample. However the presence of other phases related to iron in a lower
amount than 6 wt% cannot be excluded.

IV.3 Catalytic activity tests

In order to verify that acetic acid was converted in a heterogeneous


catalytic process, blank experiments were performed. A control test was
carried out with the reactor loaded with 250 ml of freshly prepared aqueous
solution of acetic acid with TOC of 1000 mg/l. No conversion of acetic acid
was detected during this test, indicating the necessity of the catalyst for the
observed reaction.

IV.3.1 Homogeneous catalytic Fenton oxidation

Catalytic homogeneous tests of wet oxidation with hydrogen peroxide


were carried out in a glass batch reactor under continuous stirrring in contact
with air atmosphere at T=25 °C.

46
Experimental results: Fenton oxidation of the acetic acid on FeY zeolite

IV.3.1.1 Acetic acid solution


A freshly prepared aqueous solution reaction (V=250 ml) of acetic acid
with TOC of 1000 mg/l was added to the reactor together with 1.426 g of the
catalyst (Fe(NO3)3, corresponding to a total amount of iron ions of 3.53*10-3
moles. Then a concentred solution of H2O2 was added to achieve a
H2O2/substrate stoichiometric ratio, defined as the amount of hydrogen
peroxide required to completely oxidize the substrate to CO2.
Reported in Figure 31 are the results for catalytic wet hydrogen peroxide
oxidation (CWHPO) of acetic acid with a homogeneous iron catalyst at room
temperature as a function of the time of reaction.
The total organic removal of acetic acid increases up to 30% after 4
hours.
TOC TOC removal

1200 35

30
1000

25

TOC Removal, %
800
TOC, ppm

20
600
15

400
10

200
5

0 0
0 1 2 3 4

t, h

Figure 31. Conversion as a function of time of homogeneous catalytic


reaction with acetic acid at T=25°C. Experimental conditions: pHt=0=2.67,
mcatalyst= 1.426 g.

IV.3.1.2 Real wastewater


Wastewaters derived from liming of bovine leather make up 31% of the
total amount of wastewaters. This is characterized by a high COD and high
salt content (chromium salts, sulfides, chloride ions, etc.).
The freshly prepared aqueous solution reaction (V=250 ml) of the
wastewater derived from liming with TOC of 276 mg/l was added to the
reactor together with 0.379 g of the catalyst (Fe(NO3)3, corresponding to a

47
Chapter IV

total amount of iron ions of 9.4*10-4 moles. Then a concentred solution of


H2O2 (1360 mg/l) was added.
Reported in Figure 32 are the results for catalytic wet hydrogen peroxide
oxidation (CWHPO) of the liming solution with a homogeneous iron catalyst
at room temperature as a function of the time of reaction. The conversion of
the liming solution after 4h is about 35%.

TOC TOC removal


300 40

35
250

30

200

TOC removal, %
25
TOC, ppm

150 20

15
100

10

50
5

0 0
0 1 2 3 4
t, h

Figure 32. Conversion as a function of time of a heterogeneous catalytic


reaction with liming solution at T=25°C. Experimental conditions:
pHt=0=2.0, mcatalyst= 0.379 g.

IV.3.2 Heterogeneous catalytic Fenton oxidation

Catalytic heterogeneous tests of wet oxidation on FeY with hydrogen


peroxide were carried out in a glass batch reactor under continuous stirrring
at T=25 °C or at T=70°C in contact with air atmosphere.

IV.3.2.1 Effect of reaction temperature


In order to elucidate the effect of temperature on FeY activity,
preliminarily catalytic tests were carried out at two temperatures, T=25 °C
and T=70 °C.

48
Experimental results: Fenton oxidation of the acetic acid on FeY zeolite

Summarized in Figure 33 are the results obtained using the FeY catalyst
in the following initial reaction conditions: pH=2.67, mcat = 0.170 g FeY,
T=25°C, and initial amount of H2O2 in the stoichiometric ratio with
hydrogen peroxide amount necessary to completely oxidize acetic acid to
CO2. For acetic acid this ratio is 4. The results are reported as residual TOC
as a function of the reaction time.
By monitoring Total Organic Carbon (TOC) during catalytic experiment
revealed that there is a small change in total carbon content of the solution as
shown in Figure 33. In particular, TOC removal after 4h is about 20%.

TOC TOC removal


1000 25

800 20

TOC removal, %
TOC, ppm

600 15

400 10

200 5

0 0
0 1 2 3 4
t, h

Figure 33. Conversion as a function of time of reaction in the case of the


FeY catalyst at T=25°C. Experimental conditions: pHt=0=2.67, mcatalyst=
0.170 g.
Summarized in Figure 34 are the results obtained using FeY for reaction
conditions: pH=2.67, mcat = 0.170 g FeY, T=70°C. and initial H2O2/substrate
values with respect to the stoichiometric amount of hydrogen peroxide
necessary to completely oxidize acetic acid to CO2. For acetic acid this ratio
is 4. The results are reported as residual TOC as function of reaction time at
different temperatures.
TOC removal after 4h is about 13%, which is smaller than for catalytic
tests performed at T= 25°C. This effect is probably due to a higher
decomposition rate of H2O2 (Centi et al., 2000).

49
Chapter IV

TOC TOC removal


1000 25

800 20

TOC removal, %
600 15
TOC, ppm

400 10

200 5

0 0
0 1 2 3 4
t, h

Figure 34. Conversion as a function of time of reaction in the case of the


FeY catalyst at T=70°C. Experimental conditions: pHt=0=2.67, mcatalyst=
0.170 g.

IV.3.3 Thermal analysis

Thermal analysis was carried out on the FeY sample after calcination and
after catalytic tests at 25°C and 70°C.
Results of thermal analysis performed on calcined FeY are reported in
Figure 35.

50
Experimental results: Fenton oxidation of the acetic acid on FeY zeolite
Q
100 2.0

95 1.5
3

Deriv. Weight (%/min)


Heat Flow (W/g)
90 1.0
Weight (%)

85 0.5

1
80 0.0

75 -0.5
0 200 400 600 800 1000
Exo Up Temperature (°C) Universal V3.9A TA Instruments

Figure 35. Thermal analysis performed on FeY sample before catalytic


activity test.
A high weight loss (about 20%) is observed between 20 and 300°C,
corresponding to physisorbed and held water. Over 300°C a very low loss
rate can be observed. No mass signals related to CO2 were reported.
Results of thermal analysis carried out on the FeY sample after the
catalytic activity test at 25°C are reported in Figure 36. Besides the weight
loss at temperatures lower than 200°C due to the removal of water, three
other case of weight loss with derivative weight maximum temperature
respectively of 210°C, 325°C and, lower, 475°C are observed, accompanied
by three peaks due to M/Z=44 MS signals. This phenomenon could be due
to the oxidation of organic fragment or acetic acid that remain trapped in the
zeolite after catalytic tests or a desorption of COx species, as reported in
literature (Neamtu et al., 2004).

51
Chapter IV
105 2.5

100 2.0
3

95 1.5

Deriv. Weight (%/min)


Heat Flow (W/g)
2
Weight (%)

90 1.0

85 0.5

0
80 0.0

44
75 -0.5
0 200 400 600 800 1000
Exo Up Temperature (°C) Universal V3.9A TA Instruments

Figure 36. Thermal analysis performed on FeY sample after catalytic


activity test at T=25°C in air flow.
Results of thermal analysis carried out on the FeY sample after the
catalytic activity test performed at 70°C are reported in Figure 37.

100 2.5

95 2.0

90 1.5
Deriv. Weight (%/min)
Heat Flow (W/g)
Weight (%)

85 2 1.0

80 0.5

75 0.0

70 -0.5
0 200 400 600 800 1000
Exo Up Temperature (°C) Universal V3.9A TA Instruments

Figure 37. Thermal analysis performed on FeY sample after catalytic


activity test at T=70°C in air flow.
52
Experimental results: Fenton oxidation of the acetic acid on FeY zeolite

The sample shows similar weight losses, but more intense evidencing that
the phenomenon depends on applied temperature during catalytic tests and
deeper investigation are necessaries to attribute every weight loss. By
monitoring MS signals in the range m/z = 29-210 three peaks related to CO2
release are showed.

IV.3.4 Leaching test

Leaching tests were carried out to check the potential of leaching of iron
from zeolite during catalytic tests, analysing the solution by ICP-MS. Both
iron removal from zeolite and the iron solution concentration have to be
monitored to be compared. In this case also, the solid was separated after
oxidation (T=70°C). This method allowed direct determination of the
presence of iron ions in solution.
300

280

260
Iron concentration, ppb

240

220

200

180

160

140

120

100
0 1 2 3 4 5

t, h

Figure 38. Leaching test on FeY after catalytic test at T=70°C.

The data (Figure 38) shows low dissolution (0.05 % with respect to initial
value) of iron on the zeolite at various times during acetic acid oxidation
(T=70°C).

53
V Experimental results:
characterization of the
perovskite based monolith

V.1 Sample preparation

The monolithic honeycomb perovskite-based catalyst was developed at


the Boreskov Institute of catalysis SB RAS. The perovskite structure is
showed in Figure 39.

Figure 39. Perovskite structure.


Preparation consists in supporting the active components on the
refractory carrier. Supported 3d oxides (MeOx) and perovskites (LaMeO3)
with Me = Mn, Co, Fe, Ni, Cu (Table 4) were prepared by impregnation of
thin wall (wall thickness 0.4 mm) monolithic honeycomb cordierite supports
(triangular channels of 2.5 mm size, specific area = 2 m2/g, mean pore radius
of 0.12 microns) with solutions of nitrate salts in ethylene glycol with added
citric acid. The procedure is as follows. Solutions (20 ml) of nitrate salts
(room temperature saturated nitrate solutions were mixed in required
proportions) with added citric acid (8 g in 4 ml) and ethylene glycol (2.5 ml)
were prepared and heated up to 50 °C. Monolith substrates cut as cylinders
with diameter 21–22 mm and 50 mm in height were dipped into the solution
for 5–10 min. Then, the samples were taken out of the solution, blown out by
Chapter V

air, dried in the air and calcined at 900 °C for 4 h. During the drying stage, at
100–200 °C, a film of polymerized metal–ether complexes strongly adhering
to the monolithic support walls is formed on internal and external surfaces.
After annealing at temperatures exceeding 500 °C, the organic residue is
burned, and a grainy porous perovskite-supported layer emerges.
Table 4. List of perovskite-based catalysts characterised.
Perovskite catalyst Chemical
composition
(active
phase, %)
LaMnO3 3.67
LaMnO3 2.69
LaMnO3 2.57
LaFeO3 2.24
LaNiO3 2.52
LaCoO3 2.94
LaCuO3 2.66
H2PtCl6/LaMnO3 2.69
LnFeO3/Al2O3/Zr0.9Co0.1O2 88
LnFeO3/Al2O3/Zr0.9Co0.1O2 48
H2PtCl6/Ln2O3 7.04
H2PdCl4/Ln2O3 8.17

Samples were calcined in air at 900 °C for 4h. Noble (Pt or Pd) metals (=
0.1 %) were supported by wet impregnation from different salts on the
cordierite substrate which were either pure or precovered by the oxide
sublayer. After Pt or Pd loading, samples were either directly dried under air
or, before drying, treated with hydrazine hydrate.
Perovskite oxides LnFeO3 (Ln= La2O3, CeO2,…) with triangular channels
(side 4 mm) and wall thickness (1.2 mm) were obtained by the
mechanoceramic route (Ciambelli et al., 1999). Monolith catalysts were
prepared by kneading a powdered active component with alumina based
binder (aluminium hydroxide) and zirconia doped with cobalt in acid media
followed by extrusion of the plastic pastes, drying and calcination at 900 °C
for 4 h.

V.2 Thermal analysis

Thermal analysis was carried out by the Boreskov Institute of Catalysis


(Russia) on a DQ-1500 device, (Isupova et al., 2002). Samples (200 mg)
were heated with a ramp of 10 °C/min up to 900 °C under air atmosphere.

56
Experimental Results: characterization of perovskite based monolith.

Figure 40 shows the TG, DTG and DTA curves of LaMnO3, LaCuO3,
LaCoO3, LaFeO3 and LaNiO3 perovskite precursors.
As evidenced by the DTG minima, the two samples showed initial weight
loss at temperatures lower than 120 °C due to the adsorbed water loss. The
processes of gas evolution from the precursor at air annealing are completed
only at temperatures exceeding 700 °C. Hence, this temperature was chosen
as a minimum catalyst calcination temperature.

Figure 40. Thermal analysis of perovskite precursors.

57
Chapter V

V.3 X-ray analysis

X-ray analysis was performed by the Boreskov Institute of Catalysis


(Russia) with a URD-6 diffractometer using Cu Kα radiation. The 2θ scan
region was 10–70°. Typical particle sizes were estimated from the
broadening of 400 diffraction peak (cubic index) not splitted due to
hexagonal distortion of the perovskite structure. Calcination of unsupported
LaMeO3 (Me = Fe, Mn) precursors at 900 °C leads to formation of well-
crystallized perovskite particles with typical sizes 80–100 nm. The
perovskite structure as well as cobalt, nickel and copper simple oxides
admixtures (Co3O4, NiO, CuO), respectively, were revealed in the calcined
precursors. In the case of cordierite-supported samples, the mixture of
cordierite and perovskite phases was observed after catalyst annealing at 900
°C(Figure 41), (Isupova et al., 2005).

Figure 41. X-ray diffraction patterns of cordierite carrier and supported


perovskite catalysts. P perovskite peaks; C, lanthanum oxy-carbonate peaks.
For supported lanthanum manganites and ferrites, the type of structure
(hexagonal and orthorhombic, respectively) corresponds to stable
modifications. In the case of cuprates, nickelates and cobaltites, instead of a
stable hexagonal phase, a cubic modification was revealed. Hence, for the
latter systems, pronounced interaction between the active component and the
support certainly takes places. Most probably, a part of support is dissolved
in the acidic polymerized solution at the impregnation stage (e.g. Al cations
were detected in the acidic solution after the impregnation stage), which can
be facilitated by a strong complexation ability of mixed citric acid–ethylene
glycol ethers. After precursor decomposition and calcination, a part of
aluminum cations enters into metastable perovskite-like solid solution, thus
affecting their structural properties. According to X-ray analysis particle size
of supported perovskites is in the range 30–40 nm.
X-ray microanalysis revealed that in the case of cordierite supported
catalysts prepared using the Pechini method, the cations of an active
component have a nearly uniform distribution across the wall thickness as

58
Experimental Results: characterization of perovskite based monolith.

well as forming a separate layer with 2–3 mm thickness covering the walls
of the monolithic support.

V.4 SEM analysis

The textural features of supported perovskites were studied by SEM with


a BS-350 machine by the Boreskov Institute of Catalysis (Russia) (resolution
limit is about 5–10 nm). SEM analysis (Figure 42) revealed that the active
oxide component was distributed nearly uniformly within the wall forming a
surface layer of 2-3 mm thickness which repeated the carrier surface relief.
The morphology of this porous layer composed of separate grains is nearly
independent of the calcination temperature. The supported active component
or sublayer form a grainy layer which repeats the carrier surface relief.
Separate grains compose this grainy layer, and its morphology is nearly
independent of the calcination temperature. On the wall’s cross-section a
well developed internal pore structure of cordierite and the surface layer of
supported oxides, 2–3 mm in thickness (Isupova et al., 2005).

Figure 42. SEM data on a carrier and on supported catalysts: (a) carrier,
(b) carrier+Ln2O3, (c) carrier+LaMnO3, (d) carrier+Ln2O3+LaMnO3.

59
Chapter V

V.5 Micro Raman spectroscopy

In Figure 43 Raman spectra of LaMnO3 and LaMnO3 with Pt are


reported.

LaMnO3 LaMnO3 w ith Pt


32000

2 70 0 0

22000
Counts

170 0 0

12 0 0 0

70 0 0

2000
200 300 400 50 0 600 70 0 800 900
-1
Ram an shift, cm

Figure 43. Raman spectra of LaMnO3 (3.67 %) and LaMnO3 with Pt


samples.
The Raman spectrum of LaMnO3 with Pt shows Pt species bands (411
cm-1, 391 cm-1) superimposed upon typical absorptions from the support.
In Figure 44 Raman spectra of LaFeO3 monolith and LaFeO3 powder are
reported.

60
Experimental Results: characterization of perovskite based monolith.

18000

17000
LaFeO3 monolith
16000

15000

14000
Counts

13000

12000
LaFeO3 powder
11000

10000

9000

8000
200 300 400 500 600 700 800 900
-1
Raman shift, cm

Figure 44. Raman spectra of LaFeO3 monolith and LaFeO3 powder.


The monolith and powder show bands at 310, 440, 630 cm-1.

V.6 Specific surface area

Specific surface area (SSA) was determined by a routine BET procedure


using the Ar thermal desorption data in the Boreskov Institute of Catalysis
(Russia).
The specific surface area for the prepared bulk perovskites calcined at
900 °C is 13 m2/g (for Me = Fe, Mn, Co, Ni) and 3 m2/g (for Me = Cu),
respectively.
For all supported oxides calcined at 900 °C the specific surface area is
about 2 m2/g. For all supported catalysts, the specific surface area is about 4–
6m2/g.
For the LnFeO3 monoliths, the specific surface area is about 15-20 m2/g.

V.7 NIR-UV-VIS DRS

Figure 45 depicts the diffuse reflectance UV–vis spectra of the LaMnO3


(3.67%). The Kubelka–Munk function, F(R), can be considered proportional
to the absorption of radiation (Anderson et al., 1997). A plot of the square of
the absorbed light (proportional to the square of the Kubelka-Munk function
F(R)) vs the energy of irradiation was used to obtain the band gap Eg. The
Kubelka-Munk function is given by (eq.19):
F(R) = (1 - R)2/2R) (19)
where R is the measured reflectance.

61
Chapter V

On this basis, the value of Eg, the band gap of the LaMnO3 catalyst
(3.67%) is at 2.75 eV (Figure 45).

40

35

30
(F(R)*hv)2

25

20

15

10

5
2 2,1 2,2 2,3 2,4 2,5 2,6 2,7 2,8 2,9 3 3,1 3,2 3,3 3,4 3,5 3,6 3,7 3,8
hv, eV

Figure 45. Band-gap calculus from the DR–UV–vis spectra of LaMnO3.


On this basis, the value of Eg, the band gap of the Pt/LaMnO3 catalyst is
at 2.25 eV (Figure 46).

60

50

40
(F(R)*hv)2

30

20

10

0
2 2,2 2,4 2,6 2,8 3 3,2 3,4 3,6 3,8 4
hv, ev

Figure 46. Band-gap calculus from the DR–UV–vis spectra of Pt/LaMnO3..

62
Experimental Results: characterization of perovskite based monolith.

On this basis, the value of Eg, the band gap of the LaFeO3 catalyst is at
1.90 eV (Figure 47).

20

18

16

14
2

12
(F(R)*hv)

10

0
1 1,2 1,4 1,6 1,8 2 2,2 2,4 2,6 2,8 3 3,2 3,4 3,6 3,8 4
hv, ev

Figure 47. Band-gap calculus from the DR–UV–vis spectra of LaFeO3.

On this basis, the value of Eg, the band gap of the LnFeO3 (48%) catalyst
is at 2.10 eV (Figure 48).

400

350

300

250
2
(F(R)*hv)

200

150

100

50

0
1 1,2 1,4 1,6 1,8 2 2,2 2,4 2,6 2,8 3
hv, ev

Figure 48. Band-gap calculus from the DR–UV–vis spectra of LnFeO3


(48%).

On this basis, the value of Eg, the band gap of the LnFeO3(88%) catalyst
is at 2.10 eV (Figure 49).

63
Chapter V

1200

1000

800
2
(F(R)*hv)

600

400

200

0
1 1,2 1,4 1,6 1,8 2 2,2 2,4 2,6 2,8 3
hv, ev

Figure 49. Band-gap calculus from the DR–UV–vis spectra of LnFeO3


(88%).

64
VI Experimental results: Fenton
oxidation of acetic acid on
LaMeO3 perovskite

VI.1 Catalytic activity tests

Acetic acid oxidation was carried out in a batch glass reactor of 250 ml
placed on an oscillating plate, a pH glass electrode and oxygen dissolved
(O.D.) glass electrode were used to monitor the pH and O.D.. Pieces of
structured catalysts of about 5g were tested for acetic acid oxidation in
aqueous solution (500 ppm as TOC) in the presence of H2O2 ranging
between 0.083-0.167 mol/l.

VI.1.1 Catalytic decomposition of H2O2 on LaMnO3 and LnFeO3

In the catalytic test on LaMnO3 (2.57%), with initial concentration of


hydrogen peroxide equal to 0.083 mol/l, an H2O2 consumption of 82 % is
achieved after 3 hours (Figure 50).
Chapter VI

H2O2, ppm H2O2 conversion, %


3000 100

90
2500
80

H2O2 conversion, %
70
2000
H2O2, ppm

60

1500 50

40
1000
30

20
500
10

0 0
0 1 2 3 4
t, h

Figure 50. Catalytic decomposition of H2O2 with LaMnO3 (2.57%).


Experimental conditions: pHt=o=5.3, mcatalyst= 19 g, [H2O2]t=0= 0.083 mol/l.
In Figure 51 a similar H2O2 conversion for the catalytic decomposition of
hydrogen peroxide in the presence of LnFeO3 (88%) is observed.

H2O2, ppm H2O2 conversion, %


3000 100

90
2500
80
H2O2 conversion, %
70
2000
H2O2, ppm

60

1500 50

40
1000
30
20
500
10
0 0
0 1 2 3 4 5 6
t, h

Figure 51. Catalytic decomposition of H2O2 with LnFeO3 (88%).


Experimental conditions: pHt=o=5.4, mcatalyst= 15 g, [H2O2]t=0= 0.083 mol/l.
pH increases during the reaction (Table 5). The catalysts promote the
formation of the hydroxyl radicals. The results show that the perovskite
catalysts are able to decompose H2O2 to O2 as shown by the increase of
dissolved oxygen after the test.

66
Experimental results: Fenton oxidation of acetic acid on LaMeO3 perovskite.

Table 5. pH and oxygen dissolved values for the catalytic decomposition of


hydrogen peroxide.
Catalyst pHinitial value pHfinal O.D.initial O.D.final value
value value (ppm) (ppm)
LaMnO3 5.3 6.4 - -
(2.57%)
LnFeO3 5.4 6.2 0 15
(88%)

VI.1.2 Fenton oxidation of acetic acid on LaMnO3 (3.67%)

After 5 hours (Figure 52), a poor level of CH3COOH oxidation is reached


on LaMnO3 (3.67%) shown by low TOC removal.
10 10

9 9
TOC removal, %
8 8
H2O2 conversion, %

H2O2 conversion, %
7 7
TOC removal, %

6 6

5 5

4 4

3 3

2 2

1 1

0 0
0 1 2 3 4 5 6
t,h

Figure 52. Total organic carbon removal and H2O2 conversion as a function
of time of reaction in the case of LaMnO3 (3.67%) catalyst at T=25°C.
Experimental conditions: pHt=o=3.9, mcatalyst= 4.9 g, [H2O2]t=0= 0.083 mol/l.
For the same system with higher initial H2O2 concentration, equal to
0.167 mol/l (Figure 53), only slightly higher final TOC removal is observed.
Specifically about 3% of the initial TOC disappears after t=5 hours.

67
Chapter VI

10

7
TOC removal, %

0
0 1 2 3 4 5
t, h

Figure 53. Total organic carbon removal and H2O2 conversion as a function
of time of reaction in the case of LaMnO3 (3.67%) catalyst at T=25°C.
Experimental conditions: pHt=o=3.9, mcatalyst= 4.9 g, [H2O2]t=0= 0.167 mol/l.
As a consequence, it must be pointed out that the perovskites do not
catalyse the Fenton reaction. In addition, their H2O2 decomposition ability
appears inhibited by the presence of acetic acid.

68
Experimental results: Fenton oxidation of acetic acid on LaMeO3 perovskite.

VI.1.3 Fenton oxidation of acetic acid on Pt/LaMnO3

By using LaMnO3 with Pt (Figure 54) about 10% of TOC removal is


obtained when an H2O2 consumption of 8% is achieved.
100 100

90 90
TOC removal, %
80 80

H2O2 conversion, %
70 H2O2 conversion, % 70
TOC removal, %

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 0,5 1 1,5 2 2,5 3 3,5 4
t, h

Figure 54. Total organic carbon removal and H2O2 conversion as a function
of time of reaction in the case of Pt/LaMnO3 catalyst at T=25°C.
Experimental conditions: pHt=o=3.9, mcatalyst= 6.0 g, [H2O2]t=0= 0.083 mol/l.
For the same catalyst with H2O2 concentration equal to 0.167 mol/l
(Figure 55) similar TOC removal can be obtained. Specifically, about 8% of
the initial TOC disappears after t=4 hours.

69
Chapter VI

10

7
TOC removal, %

0
0 1 2 3 4
t, h

Figure 55. Total organic carbon removal as function of time of reaction in


the case of Pt/LaMnO3 catalyst at T=25°C. Experimental conditions:
pHt=o=3.9, mcatalyst= 6.0 g, [H2O2]t=0= 0.167 mol/l.
Pt appears to promote the Fenton oxidation activity of perovskites.

VI.1.4 Fenton oxidation of acetic acid on LaFeO3 (2.24%)

In the system with LaFeO3 (2.24%) (Figure 56) about 4% of TOC


removal is quickly obtained with an H2O2 consumption of 3% after one hour.

70
Experimental results: Fenton oxidation of acetic acid on LaMeO3 perovskite.

10 10

9 9
TOC removal, %
8 H2O2 conversion, % 8

7 7

H2O2 conversion, %
TOC removal, %

6 6

5 5

4 4

3 3

2 2

1 1

0 0
0 1 2 3 4
t, h

Figure 56. Total organic carbon removal and H2O2 conversion as a function
of time of reaction in the case of LaFeO3 catalyst at T=25°C. Experimental
conditions: pHt=o=3.9, mcatalyst= 5.4 g, [H2O2]t=0= 0.083 mol/l.
The increase in H2O2 initial concentration equal to 0.167 mol/l (Figure
57),does not result in higher TOC removal; in addition, after one hour the
TOC removal is halved with respect to that obtained at lower initial H2O2
concentration.

71
Chapter VI

10 10
TOC removal, %
9 9
H2O2 conversion, %
8 8

H2O2 conversion, %
7 7
TOC removal, %

6 6

5 5

4 4

3 3

2 2

1 1

0 0
0 1 2 3 4
t, h

Figure 57. Total organic carbon removal and H2O2 conversion as a function
of time of reaction in the case of LaFeO3 catalyst at T=25°C. Experimental
conditions: pHt=o=3.9, mcatalyst= 5.4 g, [H2O2]t=0= 0.167 mol/l.

VI.1.5 Fenton oxidation of acetic acid on LaCuO3

On LaCuO3 (Figure 58) about 4% of TOC removal with a H2O2


consumption of 6% is achieved.

72
Experimental results: Fenton oxidation of acetic acid on LaMeO3 perovskite.

10 10

9 9

8 8
TOC removal, %

H2O2 conversion, %
7 H2O2 conversion, % 7
TOC removal, %

6 6

5 5

4 4

3 3

2 2

1 1

0 0
0 0,5 1 1,5 2 2,5 3 3,5 4
t, h

Figure 58. Total organic carbon removal and H2O2 conversion as a function
of time of reaction in the case of LaCuO3 catalyst at T=25°C. Experimental
conditions: pHt=o=3.9, mcatalyst= 6.4 g, [H2O2]t=0= 0.083 mol/l.
For the same system with H2O2 concentration equal to 0.167 mol/l
(Figure 59) we have similar TOC removal, specifically about 4% of the
initial TOC disappears after t=4 hours.

73
Chapter VI

10

7
TOC removal, %

0
0 1 2 3 4
t, h

Figure 59. Total organic carbon removal and H2O2 conversion as a function
of time of reaction in the case of LaCuO3 catalyst at T=25°C. Experimental
conditions: pHt=o=3.9, mcatalyst= 5.4 g, [H2O2]t=0= 0.167 mol/l.

74
Experimental results: Fenton oxidation of acetic acid on LaMeO3 perovskite.

VI.1.6 Fenton oxidation of acetic acid on LaNiO3

On LaNiO3 (Figure 60) about 4% of TOC removal is obtained when an


H2O2 consumption of 2% is achieved.
10 10

9 9

8 8
TOC removal, %

H2O2 conversion, %
7 7
H2O2 conversion, %
TOC removal, %

6 6

5 5

4 4

3 3

2 2

1 1

0 0
0 1 2 3 4
t, h

Figure 60. Total organic carbon removal and H2O2 conversion as a function
of time of reaction in the case of LaNiO3 catalyst at T=25°C. Experimental
conditions: pHt=o=3.9, mcatalyst= 6.0 g, [H2O2]t=0= 0.083 mol/l.
With higher H2O2 initial concentration (Figure 61) TOC removal rises to
about 10% after t=4 hours.

75
Chapter VI

10

7
TOC removal, %

0
0 1 2 3 4

t, h

Figure 61. Total organic carbon removal and H2O2 conversion as a function
of time of reaction in the case of LaNiO3 catalyst at T=25°C. Experimental
conditions: pHt=o=3.9, mcatalyst= 6.0 g, [H2O2]t=0= 0.167 mol/l.

76
Experimental results: Fenton oxidation of acetic acid on LaMeO3 perovskite.

VI.1.7 Fenton oxidation of acetic acid on LaCoO3

In the system with LaCoO3 (Figure 62) about 4% of TOC removal is


obtained when an H2O2 consumption of 1% is achieved.
10 10

9 9
TOC removal, %
8 H2O2 conversion, % 8

H2O2 conversion, %
7 7
TOC removal, %

6 6

5 5

4 4

3 3

2 2

1 1

0 0
0 0,5 1 1,5 2 2,5 3 3,5 4
t, h

Figure 62. Total organic carbon removal and H2O2 conversion as a function
of time of reaction in the case of LaCoO3 catalyst at T=25°C. Experimental
conditions: pHt=o=3.9, mcatalyst= 5.4 g, [H2O2]t=0= 0.087 mol/l.
For the same system with H2O2 concentration equal to 0.167 mol/l
(Figure 63) we have similar TOC removal, up to 5% after t=5 hours.

77
Chapter VI

10

7
TOC removal, %

0
0 1 2 3 4 5
t, h

Figure 63. Total organic carbon removal and H2O2 conversion as a function
of time of reaction in the case of the LaCoO3 catalyst at T=25°C.
Experimental conditions: pHt=o=3.9, mcatalyst= 5.4 g, [H2O2]t=0= 0.167 mol/l.

VI.2 Leaching test.

Leaching tests were carried out to check the potential of leaching of


metals from the perovskite during catalytic tests, analysing the solution by
ICP-AES. The solid catalyst was separated after oxidation. This method
allowed direct determination of the presence of metal ions in solution.

78
Experimental results: Fenton oxidation of acetic acid on LaMeO3 perovskite.

Table 6. Metal ion analysis of the some catalyst used for the catalytic
Fenton reaction.
Catalyst [H202]= mol/l Metal iont=0 Metal ionfinal
(ppm) time (ppm)
LaMnO3 0.083 Mn= 0 Mn= 20
(2.69%)
Pt/LaMnO3 0.083 Mn= 0 Mn= 5.7
LaFeO3 0.083 Fe= 0 Fe= 0.02
LaCuO3 0.083 Cu= 0 Cu= 4.1
LaCoO3 0.083 Co= 0 Co= 0.75
LaNiO3 0.083 Ni= 0 Ni= 0.23

The data (Table 6) show a small dissolution of the metal on the


perovskite after acetic acid oxidation.
However, Mn leaching both from LaMnO3 and Pt/LaMnO3 are significant
with respect to emission limits in EU regulations (2 ppm). Also Cu content is
higher than permitted for the discharge into surface water.

79
VII Experimental results:
photooxidation of acetic acid

VII.1 Photooxidation test conditions and typical trends

Catalytic tests were carried out feeding 250 Ncc/min air or nitrogen at the
bottom of the stainless steel sealed photoreactor.
In order to distinguish the contribution of the different reactions
participating in the photo-Fenton reaction, the following tests were
performed.
Photolysis tests of H2O2 were effected on 100 ml of solution and H2O2 in
the range 0.083-0.167 mol/l were used.
Photolysis tests of acetic acid were performed on 100 ml of solution and
acetic acid aqueous solutions containing total organic carbon concentration
(TOC) of 500 mg/l at pH 3.9.
Photolysis tests of H2O2 and CH3COOH were performed on 100 ml of
solution, H2O2 in the range 0.083-0.167 mol/l and acetic acid aqueous
solutions containing total organic carbon concentration (TOC) of 500 mg/l at
pH 3.9.
Finally, photo-Fenton tests on acetic acid aqueous solutions containing
total organic carbon concentration (TOC) of 500 mg/l at pH 3.9 and H2O2 in
the range 0.083-0.167 mol/l were carried out.
An 8 W mercury vapor lamp emitting at 254 nm was placed in the
reactor. Then the lamp was switched on and the reaction started. Very small
samples of treated solution (500 µl) were taken for analyses every hour, to
avoid changing in the contact time during the test. Gas which evolved from
the sealed photoreactor during the reaction were analysed by CO/CO2 IR
analyser (ABB) in order to verify the carbon balance.
TOC was evaluated by COX emission obtained by catalytic combustion at
T=850°C. H2O2 concentration was determined by H2O2/TiOSO4 complex (λ
= 405 nm) UV-Vis analyses (see Chapter V).
A typical trend of photocatalytic tests is reported in Figure 64 with
reference to LaMnO3 (3.67%). At the run starting time, the air or nitrogen
Chapter VII

stream was passed through the reactor in the absence of irradiation at


ambient temperature for t=10 min.
After 5 hours of irradiation, we observed TOC removal of 30% (Figure
64).

TOC removal, % H2O2 conversion, %


100 100

90 90

80 80

H2O2 conversion, %
70 70
TOC removal, %

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 0,5 1 1,5 2 2,5 3 3,5 4 4,5 5
t, h

Figure 64. Catalytic photo-Fenton oxidation in nitrogen stream on LaMnO3


(3.67%). Experimental conditions: V tot.: 100 ml; mcatalyst= 4.9 g;
C0CH3COOH= 0.021 mol/l; C0H2O2= 0.083 mol/l; P= 1 atm; T=25°C; pH=3.9,
QN2= 250 Ncc/min.

In Figure 65 the concentration of CO2 detected in the gas phase during


the photo-Fenton reaction on LaMnO3 is showed.

82
Experimental results: photooxidation of acetic acid

1000
900
800
700
CO2, ppm

600
500
400
300
200
100
0
0 50 100 150 200 250 300 350 400 450 500

t, min

Figure 65. Carbon dioxide concentration formed during catalytic photo-


Fenton oxidation in nitrogen stream on LaMnO3 (3.67%).
No formation of CO was observed. CO2 concentration reached a
maximum value of about 850 ppm, after an irradiation time of 150 min and
then decreased to 0 ppm after 500 min evidencing the stripping completion
of CO2 produced.
Moreover, from the values of TOC removal and carbon dioxide
concentration formed, the total carbon mass balance was closed to about
98%; particularly, the weight in mg of carbon evaluated from CO2 analysed
and the weight in mg of carbon evaluated from TOC removal were
respectively 28.16 and 28.69. This indicates that complete mineralization of
acetic acid is obtained in photo-Fenton oxidation.

83
Chapter VII

VII.2 Photolysis reactions

VII.2.1 Photolysis of hydrogen peroxide in absence of acetic acid

In Figure 66 it is shown that, after 5 hours, about 70% of the initial


concentration of hydrogen peroxide is converted.

H2O2 ppm H2O2 conversion


6000 100

90
5000
80

H2O2 convesrion, %
70
4000
H2O2, ppm

60

3000 50

40
2000
30

20
1000
10

0 0
0 0,5 1 1,5 2 2,5 3 3,5 4 4,5 5
t, h

Figure 66. Photolysis of H2O2 in absence of acetic acid. Experimental


conditions: V tot.: 100 ml; C0H2O2= 0.167 mol/l; P= 1 atm; T=25°C;
pH=3.9.

84
Experimental results: photooxidation of acetic acid

VII.2.2 Photolysis of hydrogen peroxide in the presence of acetic

acid

In Figure 67 it is shown that after 5 hours, in the photolysis of acetic acid


with hydrogen peroxide with a molar ratio H2O2/CH3COOH=4 about 76% of
H2O2 is converted, when TOC removal was about
35%.

TOC removal photolysis H2O2 conversion, photolysis

100 100

90 90

80 80

H2O2 conversion, %
70 70
TOC removal, %

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 1 2 3 4 5 6

t, h

Figure 67. Photolysis of H2O2 in the presence of acetic acid. Experimental


conditions: V tot.: 100 ml; H2O2/CH3COOH= 4; C0H2O2= 0.083 mol/l; P= 1
atm; T=25°C; pH=3.9.
In the presence of higher quantities of H2O2 (Figure 68) at
H2O2/CH3COOH=8, about 70% of H2O2 is converted after 5 hours. Further
H2O2 increase does not result in greater TOC conversion (35%).

85
Chapter VII

TOC removal photolysis, % H2O2 conversion photolysis, %

100 100

90 90

80 80

H2O2 conversion, %
70 70
TOC removal, %

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 1 2 3 4 5 6
t, h

Figure 68. Photolysis of H2O2 in the presence of acetic acid.


Experimental conditions: V tot.: 100 ml; H2O2/CH3COOH= 8; C0H2O2=
0.167 mol/l; P= 1 atm; T=25°C; pH=3.9.

86
Experimental results: photooxidation of acetic acid

VII.3 Photocatalytic decomposition of H2O2

VII.3.1 Homogeneous photocatalytic decomposition of H2O2

In Figure 69 it is shown, that after 4 hours, in homogeneous


photocatalytic decomposition of hydrogen peroxide (C0H2O2= 0.083 mol/l)
about 97% of H2O2 is consumed.

H2O2, ppm H2O2 conversion, %


3000 100

90
2500
80

H2O2 conversion, %
70
2000
60
H2O2, ppm

1500 50

40
1000
30

20
500
10

0 0
0 1 2 3 4 5 6 7
t, h

Figure 69. Photocatalytic decomposition of H2O2 with Fe2(C2O4)3.


Experimental conditions: V tot.: 100 ml; mcatalyst= 0.7 g; C0H2O2= 0.083
mol/l; P= 1 atm; T=25°C; pH=3.9.
In Figure 70 it is shown, that after 4 hours, in homogeneous
photocatalytic decomposition of hydrogen peroxide (C0H2O2= 0.167 mol/l)
about 95% of H2O2 is consumed with a similar reaction rate.

87
Chapter VII

H2O2, ppm H2O2 conversion, %


6000 100

90
5000
80

H2O2 conversion, %
70
4000
H2O2, ppm

60

3000 50

40
2000
30

20
1000
10

0 0
0 0,5 1 1,5 2 2,5 3 3,5 4 4,5
t, h

Figure 70. Photocatalytic decomposition of H2O2 with Fe2(C2O4)3.


Experimental conditions: V tot.: 100 ml; mcatalyst= 0.7 g; C0H2O2= 0.167
mol/l; P= 1 atm; T=25°C; pH=3.9.

VII.3.2 Heterogeneous photocatalytic decomposition of H2O2

The heterogeneous photocatalytic decomposition of H2O2, in the presence


of LaMnO3 (3.67%), with initial concentration of hydrogen peroxide equal to
0.083 mol/l, proceeds as in the absence of catalyst (Figure 71).

88
Experimental results: photooxidation of acetic acid

H2O2 LaMnO3 with H2O2 only, ppm


H2O2 conversion LaMnO3 with H2O2 only, %
3000 100

90
2500
80

H2O2 conversion, %
70
2000
H2O2, ppm

60

1500 50

40
1000
30

20
500
10

0 0
0 1 2 3 4 5 6
t, h

Figure 71. Photocatalytic decomposition of H2O2 with LaMnO3 (3.67%).


Experimental conditions: V tot.: 100 ml; mcatalyst= 4.9 g; C0H2O2= 0.083
mol/l; P= 1 atm; T=25°C; pH=3.9.
In the same system with initial concentration of hydrogen peroxide equal
to 0.167 mol/l, (Figure 72) a higher hydrogen peroxide conversion is noted.
H2O2, ppm H2O2 conversion, %
6000 10 0

90
50 0 0
80
H2O2 conversion, %

70
4000
H2O2, ppm

60

3000 50

40
2000
30

20
10 0 0
10

0 0
0 1 2 3 4 5
t, h

Figure 72. Photocatalytic decomposition of H2O2 with LaMnO3 (3.67%).


Experimental conditions: V tot.: 100 ml; mcatalyst= 4.9 g; C0H2O2= 0.167
mol/l; P= 1 atm; T=25°C; pH=3.9.

89
Chapter VII

In the photo-system Pt/LaMnO3, with initial concentration of hydrogen


peroxide equal to 0.083 mol/l, an H2O2 consumption of 52 % is achieved
after 3 hours (Figure 73).

H2O2, ppm H2O2 conversion, %


3000 100

90
2500
80

H2O2 conversion, %
70
2000
H2O2, ppm

60

1500 50

40
1000
30

20
500
10

0 0
0 1 2 3 4
t, h

Figure 73. Photocatalytic decomposition of H2O2 with Pt/LaMnO3.


Experimental conditions: V tot.: 100 ml; mcatalyst= 6.0 g; C0H2O2= 0.083
mol/l; P= 1 atm; T=25°C; pH=3.9.
In the same system with initial concentration of hydrogen peroxide equal
to 0.167 mol/l, (Figure 74) a higher hydrogen peroxide conversion is noted.

90
Experimental results: photooxidation of acetic acid

H2O2, ppm H2O2 conversion, %


6000 100

90
5000
80

H2O2 conversion, %
70
4000
H2O2, ppm

60

3000 50

40
2000
30

20
1000
10

0 0
0 0,5 1 1,5 2 2,5 3 3,5 4 4,5
t, h

Figure 74. Photocatalytic decomposition of H2O2 with Pt/LaMnO3.


Experimental conditions: V tot.: 100 ml; mcatalyst= 6.0 g; C0H2O2= 0.167
mol/l; P= 1 atm; T=25°C; pH=3.9.

VII.4 Photocatalytic decomposition of acetic acid

In the photo/LaMnO3, in the presence of acetic acid only with the initial
concentration of the acetic acid equal to 0.010 mol/l, a TOC removal of 7 %
is achieved after 1 hour (Figure 75), and then remains constant.

91
Chapter VII

TOC removal LaMnO3 with acetic acid only , %


50

45

40

35
TOC removal, %

30

25

20

15

10

0 1 2 3
t, h

Figure 75. Photocatalytic decomposition of acetic acid with LaMnO3


(3.67%). Experimental conditions: V tot.: 100 ml; mcatalyst= 4.9 g; TOCt=0=
250 ppm; P= 1 atm; T=25°C; pH=3.9.
In the same system, in the presence of acetic acid only with initial
concentration of the acetic acid equal to 0.021 mol/l, a slightly lower
conversion of about 6% is achieved (Figure 76), after 2 hours.

TOC rem oval of acetic acid w ith acetic acid only, %


6

5
TOC removal, %

0
0 1 2 3 4 5 6

t, h

Figure 76. Photocatalytic decomposition of acetic acid with LaMnO3


(3.67%). Experimental conditions: V tot.: 100 ml; mcatalyst= 4.9 g; TOCt=0=
500 ppm; P= 1 atm; T=25°C; pH=3.9.

92
Experimental results: photooxidation of acetic acid

VII.5 Catalyst samples for photo-Fenton tests

A list of catalysts tested in CH3COOH photo-Fenton oxidation is reported


in Table 7.
The monolithic honeycomb perovskite-based catalysts were prepared by
the Boreskov Institute of catalysis SB RAS and were previously described
(see Chapter V). Powder perovskites were also tested for comparison.
Fe2(C2O4)3 was chosen as the reference homogeneous catalyst.
Table 7. List of catalysts tested.
Perovskite catalyst Chemical Catalyst kind-form
composition
(active
phase, %)
LaMnO3 3.67 Supported-Structured
LaMnO3 2.69 Supported-Structured
LaMnO3 2.57 Supported-Structured
LaMnO3 100 Bulk-Powder
LaFeO3 2.24 Supported-Structured
LaFeO3 100 Bulk-Powder
LaNiO3 2.52 Supported-Structured
LaCoO3 2.94 Supported-Structured
LaCuO3 2.66 Supported-Structured
H2PtCl6/LaMnO3 2.69 Supported-Structured
LnFeO3/Al2O3/Zr0.9Co0.1O2 88 Bulk-Supported-Structured
LnFeO3/Al2O3/Zr0.9Co0.1O2 48 Bulk-Supported-Structured
H2PtCl6/Ln2O3 7.04 Bulk-Supported-Structured
H2PdCl4/Ln2O3 8.17 Bulk-Supported-Structured

VII.6 Catalytic photo-Fenton oxidation

VII.6.1 Homogeneous photo-Fenton oxidation

For the photo-ferrioxalate system with H2O2/CH3COOH=4, about 24% of


the initial TOC disappears when an H2O2 consumption of up to 90 % was
achieved (Figure 77).

93
Chapter VII

TOC removal homogeneous photoFenton


H2O2 conversion homogeneous photoFenton
100 100
90 90
80 80

H2O2 conversion, %
70 70
TOC removal, %

60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 1 2 3 4 5
t, h

Figure 77. Homogeneous photo-Fenton with Fe2(C2O4)3. Experimental


conditions: V tot.: 100 ml; mcatalyst= 0.7 g; C0CH3COOH= 0.021 mol/l; C0H2O2=
0.083 mol/l; P= 1 atm; T=25°C; pH=3.9.

94
Experimental results: photooxidation of acetic acid

VII.6.2 Heterogeneous photo-Fenton oxidation

VII.6.2.1 Heterogeneous photo-Fenton oxidation on


LaMnO3 (3.67%)
With the heterogeneous structured catalyst LaMnO3 (3.67%), about 54 %
of TOC removal is obtained within 5 hours and higher H2O2 consumption
(96 %) also with respect to H2O2 photolysis (Figure 78). TOC removal ends
when all H2O2 is consumed.

TOC removal, LaMnO3 H2O2 conversion, LaMnO3


100 100

90 90

80 80

H2O2 conversion, %
70 70
TOC removal, %

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 1 2 3 4 5 6
t, h

Figure 78. Heterogeneous photo-Fenton with LaMnO3 (3.67%).


Experimental conditions: V tot.: 100 ml; mcatalyst= 4.9 g; C0CH3COOH= 0.021
mol/l; C0H2O2= 0.083 mol/l; P= 1 atm; T=25°C; pH=3.9.
When a molar ratio of H2O2/CH3COOH=8 is used, about 59 % of TOC
removal is obtained with almost total H2O2 consumption (Figure 79).

95
Chapter VII

TOC removal, LaMnO3


H2O2 conversion, LaMnO3
100 100

90 90

80 80

H2O2 conversion, %
70 70
TOC removal, %

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 1 2 3 4 5 6

t, h

Figure 79. Heterogeneous photo-Fenton with LaMnO3 (3.67%).


Experimental conditions: V tot.: 100 ml; mcatalyst= 4.9 g; C0CH3COOH= 0.021
mol/l; C0H2O2= 0.167 mol/l; P= 1 atm; T=25°C; pH=3.9.

96
Experimental results: photooxidation of acetic acid

VII.6.2.2 Heterogeneous photo-Fenton oxidation on


Pt/LaMnO3
In the photo/Pt/LaMnO3 system with H2O2/CH3COOH=4, about 54 % of
TOC removal is obtained when an H2O2 consumption of 98 % is achieved
(Figure 80).

TOC removal,Pt/ LaMnO3


H2O2 conversion, LaMnO3
100 100
90 90

H2O2 conversion, %
80 80
TOC removal, %

70 70
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 1 2 3 4 5 6
t, h

Figure 80. Heterogeneous photo-Fenton with LaMnO3 with Pt.


Experimental conditions: V tot.: 100 ml; mcatalyst= 6.0 g; C0CH3COOH= 0.021
mol/l; C0H2O2= 0.083 mol/l; P= 1 atm; T=25°C; pH=3.9.
In the photo-Pt/LaMnO3 system, no significant increase was obtained by
employing H2O2/CH3COOH=8, 55 % of TOC removal and an H2O2
consumption of 99 %, was also achieved (Figure 81).

97
Chapter VII

TOC removal, Pt/LaMnO3


H2O2 conversion,Pt/LaMnO3
100 100

90 90

80 80

H2O2 conversion, %
70 70
TOC removal, %

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 1 2 3 4 5 6
t, h

Figure 81. Heterogeneous photo-Fenton with LaMnO3 with Pt.


Experimental conditions: V tot.: 100 ml; mcatalyst= 6.0 g; C0CH3COOH= 0.021
mol/l; C0H2O2= 0.167 mol/l; P= 1 atm; T=25°C; pH=3.9.

VII.6.2.3 Heterogeneous photo-Fenton oxidation on


LaFeO3 (2.24%)
In the photo/LaFeO3 (2.24%) system with H2O2/CH3COOH=4, about 60
% of TOC removal is obtained when an H2O2 consumption of 90 % is
achieved (Figure 82).

98
Experimental results: photooxidation of acetic acid

TOC rem oval LaFeO3, % H2O2 conversion, LaFeO3, %


10 0 10 0

90 90

80 80

H2O2 conversion, %
TOC removal, %

70 70

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 1 2 3 4 5 6
t, h

Figure 82. Heterogeneous photo-Fenton with LaFeO3 (2.24%).


Experimental conditions: V tot.: 100 ml; mcatalyst= 5.4 g; C0CH3COOH= 0.021
mol/l; C0H2O2= 0.083 mol/l; P= 1 atm; T=25°C; pH=3.9.

VII.6.2.4 Heterogeneous photo-Fenton oxidation on


LaCuO3
In the photo/LaCuO3 system with H2O2/CH3COOH=4, about 65 % of
TOC removal is obtained when an H2O2 consumption of 100 % is achieved
(Figure 83).

99
Chapter VII

TOC removal, LaCuO3 H2O2 conversion, LaCuO3


100 100

90 90

80 80

H2O2 conversion, %
70 70
TOC removal, %

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 1 2 3 4 5 6 7
t, h

Figure 83. Heterogeneous photo-Fenton with LaCuO3. Experimental


conditions: V tot.: 100 ml; mcatalyst= 6.4 g; C0CH3COOH= 0.021 mol/l; C0H2O2=
0.083 mol/l; P= 1 atm; T=25°C; pH=3.9.

VII.6.2.5 Heterogeneous photo-Fenton oxidation on


LaCoO3
In the photo/LaCoO3 system with H2O2/CH3COOH=4, about 52 % of
TOC removal is obtained when an H2O2 consumption of 87 % is achieved
(Figure 84).

100
Experimental results: photooxidation of acetic acid

TOC removal, LaCoO3 H2O2 conversion, LaCoO3

100 100

90 90

80 80

H2O2 conversion, %
70 70
TOC removal, %

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 1 2 3 4 5 6 7

t, h

Figure 84. Heterogeneous photo-Fenton with LaCoO3. Experimental


conditions: V tot.: 100 ml; mcatalyst= 5.4 g; C0CH3COOH= 0.021 mol/l; C0H2O2=
0.083 mol/l; P= 1 atm; T=25°C; pH=3.9.

VII.6.2.6 Heterogeneous photo-Fenton oxidation on


LaNiO3
In the photo/LaNiO3 system with H2O2/CH3COOH=4, about 49 % of
TOC removal is obtained when an H2O2 consumption of 89 % is achieved
(Figure 85).

101
Chapter VII

TOC removal, LaNiO3 H2O2, conversion, LaNiO3


100 100

90 90

80 80

H2O2 conversion, %
TOC removal, %

70 70

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 1 2 3 4 5 6
t, h

Figure 85. Heterogeneous photo-Fenton with LaNiO3. Experimental


conditions: V tot.: 100 ml; mcatalyst= 6.0 g; C0CH3COOH= 0.021 mol/l; C0H2O2=
0.083 mol/l; P= 1 atm; T=25°C; pH=3.9.

102
Experimental results: photooxidation of acetic acid

VII.6.2.7 Heterogeneous photo-Fenton oxidation on


LnFeO3 (48%)
In the photo/LnFeO3 system with H2O2/CH3COOH=4, about 40 % of
TOC removal is obtained when an H2O2 consumption of 100 % is achieved
(Figure 86).

TOC removal, % H2O2 conversion, %


100 100

90 90

80 80

H2O2 conversion, %
TOC removal, %

70 70

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 1 2 3 4 5 6
t, h

Figure 86. Heterogeneous photo-Fenton with LnFeO3 (48%). Experimental


conditions: V tot.: 100 ml; mcatalyst= 14.0 g; C0CH3COOH= 0.021 mol/l; C0H2O2=
0.083 mol/l; P= 1 atm; T=25°C; pH=3.9.

VII.6.2.8 Heterogeneous photo-Fenton oxidation on


LnFeO3 (88%)
In the presence of the catalyst with a high load of perovskite a lower
conversion is noted, particularly about 29 % of TOC removal is obtained
when an H2O2 consumption of 100 % is achieved (Figure 87).

103
Chapter VII

TOC removal, % H2O2 conversion, %


100 100

90 90

80 80

H2O2 conversion, %
TOC removal, %

70 70

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 0,5 1 1,5 2 2,5 3 3,5 4
t, h

Figure 87. Heterogeneous photo-Fenton with LnFeO3 (88%). Experimental


conditions: V tot.: 100 ml; mcatalyst= 15.3 g; C0CH3COOH= 0.021 mol/l; C0H2O2=
0.083 mol/l; P= 1 atm; T=25°C; pH=3.9.
For bulk structured ferrites, faster H2O2 and TOC conversion were
observed, since their concentration levelled off after 2 hours. Maximum
TOC removal appears limited by H2O2 consumption.

VII.6.2.9 Heterogeneous photo-Fenton oxidation on


Pt/Ln2O3
In the photo-Pt/Ln2O3 system with H2O2/CH3COOH=4, about 46 % of
TOC removal is obtained when an H2O2 consumption of 94 % is achieved
(Figure 88).

104
Experimental results: photooxidation of acetic acid

TOC removal, % H2O2 conversion, %


100 100

90 90

80 80

H2O2 conversion, %
TOC removal, %

70 70

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 1 2 3 4 5
t, h

Figure 88. Heterogeneous photo-Fenton with Pt/Ln2O3. Experimental


conditions: V tot.: 100 ml; mcatalyst= 4.4 g; C0CH3COOH= 0.021 mol/l; C0H2O2=
0.083 mol/l; P= 1 atm; T=25°C; pH=3.9.

VII.6.2.10 Heterogeneous photo-Fenton oxidation on


Pd/Ln2O3
In the photo-Pd/Ln2O3 system, with H2O2/CH3COOH=4, about 47 % of
TOC removal is obtained when an H2O2 consumption of 94 % is achieved
(Figure 89).

105
Chapter VII

TOC removal, % H2O2 conversion, %


50 100
45 90

H2O2 conversion, %
TOC removal, % 40 80
35 70
30 60
25 50
20 40
15 30
10 20
5 10
0 0
0 1 2 3 4 5 6

t, h

Figure 89. Heterogeneous photo-Fenton with Pd/Ln2O3. Experimental


conditions: V tot.: 100 ml; mcatalyst= 4.4 g; C0CH3COOH= 0.021 mol/l; C0H2O2=
0.083 mol/l; P= 1 atm; T=25°C; pH=3.9.

VII.7 Thermal analysis

Results of thermal analysis carried out on the LaMnO3 (2.69%) sample


before and after a catalytic activity test at 25°C is reported in Figure 90. A
high weight loss of the catalyst used is observed between 20 and 300°C,
corresponding to physisorbed and held water.
Other weight loss with derivative weight maximum temperature, 345°C is
observed.
This phenomenon could be due to the oxidation of the organic fragments
or the acetic acid that remained adsorbed on the perovskite after catalytic
tests.

106
Experimental results: photooxidation of acetic acid

105 4
––––––– La MnO3 before test
–––– La MnO3 after test
100 0.2 3

Deriv. Weight (%/min)


Heat Flow (W/g)
95 0.0 2
Weight (%)

90 -0.2 1

85 -0.4 0

80 -1
0 200 400 600 800
Temperature (°C)

Figure 90. Thermal analysis performed on the LaMnO3 (2.69%) sample


before and after the catalytic activity test.

VII.8 Catalytic activity comparison

VII.8.1 Heterogeneous vs homogeneous Photo-Fenton

Figure 91 shows higher total organic removal for heterogeneous photo-


Fenton with respect to homogeneous photo-Fenton.

107
Chapter VII

60 LaFeO3
LaMnO3

50 LaNiO3 Ln2O3 -Pd

LaMnO3-Pt Ln2O3 - Pt

40 LaCoO3
TOC removal, %

LaCuO3
30

Fe2(C2O4)3
20

10

0
0 1 2 3 4 5 6
t, h

Figure 91. Heterogeneous vs homogeneous photo-Fenton.


Heterogeneous catalysts show higher TOC removal efficiency, despite
the fact that the homogeneous catalyst is faster in a shorter reaction time.
However, Fe2+ activity appears to decrease after one hour reaching a lower
final degree of TOC reduction with respect to the catalysts, both
heterogeneous perovskites and rare earth oxides.
The most interesting catalysts are LaFeO3 and LaMnO3 and LaNiO3. The
addition of Pd and Pt does not significantly enhance catalytic performance,
and so it is more economically convenient not to use noble metals.
Because of the higher environmental compatibility of Fe and Mn, for
which regulated emissions are 2 ppm, the following studies have focused on
LaFeO3 and LaMnO3.

108
VIII Experimental results:
photo-Fenton oxidation of acetic
acid on LaMnO3, LaFeO3 and
LnFeO3

VIII.1.1 Comparison of catalytic activity of the monolith with

respect to powder catalysts

Photo-Fenton CH3COOH oxidation has also been performed on powder


catalysts in order to observe the presence of diffusive phenomena. A test was
performed on supported LaMnO3 monolith powdered on an agate grinder.
Figure 93 shows higher total organic removal (about 55%) on the
monolith with respect to the powder catalyst supported (about 43%) with
H2O2 consumption of 100 %, although after 1 h TOC removal is higher for
the powder catalyst.
Chapter VIII

TOC rem oval m onolith, % TOC rem oval pow der, %


H2O2 conversion m onolith, % H2O2 conversion pow der, %

10 0 10 0
90 90
80 80

H2O2 conversion, %
TOC removal %

70 70
60 60
50 50
40 40
30 30

20 20
10 10
0 0
0 1 2 3 4
t, h

Figure 92. Comparison of catalytic activity of the monolith LaMnO3


(2.69%) with respect to powdered catalyst. Experimental conditions: V tot.:
100 ml; mcatalyst= 6.0 g; C0CH3COOH= 0.021 mol/l; C0H2O2= 0.083 mol/l; P= 1
atm; T=25°C; pH=3.9.

A second experiment was performed by using a perovskite powder in a


similar amount to that present on the monolith piece; by considering 2.69%
of the supported perovskites on a monolith fragment of 6.0 g, it can be
evaluated that 184 mg of LaMnO3 have to be employed.
Figure 93 shows higher total organic removal (about 55%) for the
monolith with respect to the powder perovskite (about 52%) when H2O2
consumption of 100 % is achieved.

110
Experimental results: photo-Fenton oxidation of acetic acid on LaMnO3, LaFeO3 and LnFeO3

TOC removal monolith, % TOC removal powder, %


H2O2 conversion monolith, % H2O2 conversion powder, %

100 100

90 90

80 80

H2O2 conversion, %
TOC removal %

70 70

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 0,5 1 1,5 2 2,5 3 3,5 4
t, h

Figure 93. Comparison of catalytic activity of the monolith LaMnO3


(2.69%) with respect to powder not supported. Experimental conditions: V
tot.: 100 ml; mcatalyst (monolith)= 5.0 g; mcatalyst (powder)= 0.184 g; C0CH3COOH=
0.021 mol/l; C0H2O2= 0.083 mol/l; P= 1 atm; T=25°C; pH=3.9.
In the same way LaFeO3 powder was tested and the comparison reported
in Figure 94. Same total organic removal (about 54%) for the monolith and
the powder LaFeO3 catalyst. A higher H2O2 consumption for the powder was
observed.
Photo-Fenton heterogeneous activity resulted unaffected by diffusional
limitations, the effected tests proceeded in chemical regime and
photoactivity is to be ascribed to the perovskite phase in wich the active
phase for the reaction took place.

111
Chapter VIII

TOC removal LaFeO3 monolith, %


TOC removal LaFeO3 powder, %
H2O2 conversion LaFeO3 monolith, %
H2O2 conversion LaFeO3 powder, %
100 100

90 90

80 80

H2O2 conversion, %
70 70
TOC removal, %

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 1 2 3 4
t, h

Figure 94. Comparison of catalytic activity of the monolith LaFeO3 with


respect to powder. Experimental conditions: V tot.: 100 ml; mcatalyst (monolith)=
6.0 g; mcatalyst (powder)= 0.122 g; C0CH3COOH= 0.021 mol/l; C0H2O2= 0.083 mol/l;
P= 1 atm; T=25°C; pH=3.9.

VIII.1.2 Effect of mass catalyst

Figure 95 shows lower total organic removal (about 35%) for the test
with a higher mass monolith, when an H2O2 consumption of 100 % is
achieved.

112
Experimental results: photo-Fenton oxidation of acetic acid on LaMnO3, LaFeO3 and LnFeO3

TOC removal, m=14 g %


H2O2 conversion, m=4.9 g %
H2O2 conversion, m=14 g %
TOC removal m=4.9 g, %
100 100
90 90

H2O2 conversion, %
80 80
TOC removal, %

70 70
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 0,5 1 1,5 2 2,5 3 3,5 4
t, h

Figure 95. Comparison of catalytic activity of the monolith LaMnO3


(2.57%) with different mass. Experimental conditions: V tot.: 100 ml;
mcatalyst= 14.0 g – 4.9 g; C0CH3COOH= 0.021 mol/l; C0H2O2= 0.083 mol/l; P= 1
atm; T=25°C; pH=3.9.
Higher catalyst mass leads to faster H2O2 consumption, since the
perovskite is able to catalyse its decomposition (see Chapter VII, par. VII.3).

VIII.1.3 Effect of pH

Figure 96 shows the effect of pH reactions on the catalytic activity of


monolith LaMnO3 (3.67%); particularly, by increasing the pH to pH=6, the
total organic removal goes up to about 57%. Raising the pH further (equal to
8) brings total organic removal down 22%. At pH=6, H2O2 conversion is
slower than at pH=3.9, while in more basic conditions, decomposition is
faster but incomplete (70%).

113
Chapter VIII

TOC removal pH=3.9, % TOC removal pH=6.0, %


TOC removal pH=8, % H2O2 conversion pH=3.9, %
H2O2 conversion pH=6, % H2O2 conversion pH=8, %
100 100
90 90
80 80

H2O2 conversion, %
TOC removal, %

70 70
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 1 2 3 4 5 6 7

t, h

Figure 96. Effect of pH reaction on catalytic activity of monolith LaMnO3


(3.67%). Experimental conditions: V tot.: 100 ml; mcatalyst= 4.9 g;
C0CH3COOH= 0.021 mol/l; C0H2O2= 0.083 mol/l; P= 1 atm; T=25°C.
At lower perovskite contents, on monolith LaMnO3 (2.59%), the pH
increase (pH=7), causes a decrease in total organic removal at 35% (Figure
97), due to faster H2O2 consumption.

114
Experimental results: photo-Fenton oxidation of acetic acid on LaMnO3, LaFeO3 and LnFeO3

TOC removal pH=3.9, % TOC removal pH=7.0, %


H2O2 conversion pH=3.9, % H2O2 conversion pH=7.0, %

100 100

90 90

80 80

H2O2 conversion, %
70 70
TOC removal, %

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 0,5 1 1,5 2 2,5 3
t, h

Figure 97. Effect of pH reaction on catalytic activity of monolith LaMnO3


(2.69%). Experimental conditions: V tot.: 100 ml; mcatalyst= 5.6 g;
C0CH3COOH= 0.021 mol/l; C0H2O2= 0.083 mol/l; P= 1 atm; T=25°C.

115
Chapter VIII

VIII.1.4 Effect of H2O2 concentration

By increasing molar ratio R=H2O2/CH3COOH, the initial TOC removal


rate decreases while final TOC abatement increases (Figure 98).
Higher H2O2 conversion for R=2.

TOC removal, R=4, % TOC removal, R=8, %


TOC removal, R=2, % H2O2 conversion, R=4, %
H2O2 conversion, R=8, % H2O2 conversion, R=2, %
70 100

90
60
80

50 70

H2O2 conversion, %
TOC removal, %

60
40

50

30
40

20 30

20
10
10

0 0
0 1 2 3 4 5 6
t, h

Figure 98. Comparison of catalitic activity on LaMnO3 (3.67%) on


changing H2O2. concentration.
A lower H2O2/CH3COOH ratio results in faster H2O2 conversion. When
H2O2 is totally consumed, the reaction stops, giving a stabilization in the
TOC value.

116
Experimental results: photo-Fenton oxidation of acetic acid on LaMnO3, LaFeO3 and LnFeO3

VIII.1.5 Effect of dosage of H2O2

To render the photo-Fenton processes competitive with other processes, it


is essential that their applications represent a low cost operation, which
basically implies a low consumption of H2O2 dosage. Controlled
concentration of H2O2 permits higher TOC reductions in shorter times,
owing to the H2O2 auto-scavenger effect that traps OH. generated by
photolysis according to reactions 15-17 of Chapter II. OH. radicals react with
H2O2 to form HO2. which couples with itself to give O2 and H2O2. As a
consequence, high initial levels of H2O2 do not lead to that can be employed
OH. useful for the photo-Fenton reaction, but low levels do not produce
sufficient OH. for the reaction. So it seems necessary to perform the reaction
with an adjusted concentration of H2O2 during all of the reaction time. To
this purpose, the objective of this evaluation is to select the best operational
dosage of H2O2 in photo-Fenton processes.
To realise these operative conditions, step addition of H2O2 was
performed, by adding small volumes of concentrated solution of H2O2 each
hour. Figure 99 reports the typical trend thus obtained of H2O2
concentrations, resulting in a saw tooth profile. Levels of H2O2
concentrations lay in a value range that in this case is comprised between
210 and 850 ppm. For the photo-Fenton process on LaMnO3 (3.67%), the
global mean addition of H2O2 is equal to 0.009 M/h. Total organic removal
of up to 70% was achieved.

TOC removal LaMnO3 with H2O2 added, % H2O2, ppm

100 1200
90
1000
80
TOC removal, %

70
800
H2O2, ppm

60
50 600
40
400
30
20
200
10
0 0
0 1 2 3 4 5 6
t, h

Figure 99. Effect of dosage of H2O2 on the catalytic activity of LaMnO3


(3.67%). Experimental conditions: V tot.: 100 ml; mcatalyst= 4.9 g;
C0CH3COOH= 0.021 mol/l; C0H2O2= 0.014 mol/l; CH2O2/t= 0.009 M/h; P= 1
atm; T=25°C.

117
Chapter VIII

In the photo-Fenton process with LnFeO3 (48%) (Figure 100), the


addition of H2O2 equal to 0.006 M/h increases total organic removal from
40% (H2O2/CH3COOH =4) to 76%.
TOC removal LnFeO3 (48%) with H2O2 added, % H2O2, ppm

100 500

90 450

80 400
TOC removal, %

70 350

H2O2, ppm
60 300

50 250

40 200

30 150

20 100

10 50

0 0
0 1 2 3 4 5 6
t, h

Figure 100. Effect of dosage of H2O2 on the catalytic activity of LnFeO3


(48%). Experimental conditions: V tot.: 100 ml; mcatalyst= 14 g; C0CH3COOH=
0.021 mol/l; C0H2O2= 0.012 mol/l; CH2O2/t= 0.006 M/h; P= 1 atm; T=25°C.
In the photo-Fenton process with LnFeO3 (88%) (Figure 101), the global
mean addition of H2O2 equal to 0.022 M/h increases total organic removal
from 29% obtained at initial molar ratio H2O2/CH3COOH =4 up to 100%.

TOC rem oval LnFeO3 (88%) w ith H2O2 added, % H2O2, ppm
10 0 150 0

90
13 0 0
80
110 0
TOC removal, %

70
900
H2O2, ppm

60

50 70 0

40
50 0
30
300
20

10 10 0

0 - 10 0
0 1 2 3 4 5 6
t, h

Figure 101. Effect of dosage of H2O2 on the catalytic activity of LnFeO3


(88%). Experimental conditions: V tot.: 100 ml; mcatalyst= 15.3 g; C0CH3COOH=
0.021 mol/l; C0H2O2= 0.022 mol/l; CH2O2/t= 0.021 M/h; P= 1 atm; T=25°C.

118
Experimental results: photo-Fenton oxidation of acetic acid on LaMnO3, LaFeO3 and LnFeO3

Table 8 shows a comparison of hydrogen peroxide consumption of the


photo-Fenton of LaMnO3 (3.67%) with step dosage of H2O2 with respect to
the photo/LaMnO3 system that starts with H2O2/CH3COOH=4. There is a
smaller hydrogen peroxide consumption in presence of dosage of hydrogen
peroxide with respect to the photo/LaMnO3 system without dosage.
Particularly it is noted that a higher final total organic carbon removal (70%)
in the presence of dosage of hydrogen peroxide with respect to the
photo/LaMnO3 system with initial molar ratio H2O2/CH3COOH=4 (54 %).
Moreover, a smaller specific consumption defined by molar ratio
H2O2/CH3COOH is noted; specifically, it is ranged 1.7 mol/mol (2.2
gH2O2/gC) 3.3 mol/mol (4.8 gH2O2/gC) in the test with dosage, while it is
ranged between 2.0 mol/mol (2.8 gH2O2/gC) and 7.5 mol/mol (10.8 gH2O2/gC)
in the test without dosage.

Table 8. Comparison of hydrogen peroxide consumption of the photo-


Fenton of LaMnO3 (3.67%) with dosage of H2O2 with respect to the
photo/LaMnO3 system with H2O2/CH3COOH=4.
TOC Dosage Dosage No dosage No Dosage
removal, H2O2 H2O2 cons., H2O2 cons., H2O2 cons.,
% consumption, gH2O2/gc ppm gH2O2/gc
ppm
20 222 2.2 283 2.8

50 1204 4.8 2689 10.8

70 1683 4.8 - -

Table 9 shows a comparison of hydrogen peroxide consumption of the


photo-Fenton of LnFeO3 (48%) with dosage of H2O2 with respect to the
photo/LnFeO3 system with H2O2/CH3COOH=4. There is lower hydrogen
peroxide consumption in the presence of dosage of hydrogen peroxide with
respect to the photo/LnFeO3 system with H2O2/CH3COOH=4. To be specific
a higher final total organic carbon removal (76%) is noted in the presence of
dosage of hydrogen peroxide with respect to the photo/LnFeO3 system with
H2O2/CH3COOH=4 (40 %). Moreover, a smaller specific consumption is
noted defined by molar ratio H2O2/CH3COOH; specifically, it is varied in the
1.0 mol/mol (1.5 gH2O2/gC) 3.1 mol/mol (4.4 gH2O2/gC) range in the test with
dosage, while it reaches a value equal to 12.6 mol/mol (17.9 gH2O2/gC) in the
test without dosage.

119
Chapter VIII

Table 9. Comparison of hydrogen peroxide consumption of the photo-


Fenton of LnFeO3 (48%) with dosage of H2O2 with respect to the
photo/LnFeO3 system with H2O2/CH3COOH=4.
TOC Dosage Dosage No dosage No Dosage
removal, H2O2 H2O2 cons., H2O2 cons., H2O2 cons.,
% consumption, gH2O2/gc ppm gH2O2/gc
ppm
30 222 1.5 2689 17.9

50 1204 4.8 - -

76 1683 4.4 - -

The Table 10 shows a comparison of hydrogen peroxide consumption of


the photo-Fenton of LnFeO3 (88%) with dosage of H2O2 with respect to the
photo/LnFeO3 system with H2O2/CH3COOH=4. There is lower hydrogen
peroxide consumption in the presence of dosage of hydrogen peroxide with
respect to the photo/LnFeO3 system with H2O2/CH3COOH=4. Particularly
higher final total organic carbon removal (100%) is noted in the presence of
dosage of hydrogen peroxide with respect to the photo/LnFeO3 system with
H2O2/CH3COOH=4 (30 %). Moreover, smaller specific consumption is
noted defined by molar ratio H2O2/CH3COOH; particularly, it is varied in the
3.1 mol/mol (4.5 gH2O2/gC) 5.3 mol/mol (7.6 gH2O2/gC) range in the test with
dosage, while it results equal to 18.0 mol/mol (26.4 gH2O2/gC) in the test
without dosage.

Table 10. Comparison of hydrogen peroxide consumption of the photo-


Fenton of LnFeO3 (88%) with dosage of H2O2 with respect to the
photo/LnFeO3 system with H2O2/CH3COOH=4.
TOC Dosage Dosage No dosage No Dosage
removal, H2O2 H2O2 cons., H2O2 cons., H2O2 cons.,
% consumption, gH2O2/gc ppm gH2O2/gc
ppm
20 446 4.5 2604 26.4

60 2453 8.2 - -

100 3814 7.6 - -

120
Experimental results: photo-Fenton oxidation of acetic acid on LaMnO3, LaFeO3 and LnFeO3

VIII.2 Leaching test

Leaching tests were carried out to check the potential of leaching of the
metals from the perovskite during the catalytic tests, analysing the solution
by ICP-AES. This method allowed direct determination of the presence of
metal ions in solution.
Table 11. Metal ion analysis of the some catalysts used for the catalytic
photo-Fenton reaction.
Catalyst [H202]= pH Metal Metal
mol/l iont=0 ionfinal time
(ppm) (ppm)
LaMnO3 0.083 3.9 Mn= 0 Mn= 14
(3.67%)
LaMnO3 0.083 7.0 Mn= 0 Mn= 0.03
(3.67%)
LaMnO3 0.083 8.0 Mn= 0 Mn= 0.19
(3.67%)
LaMnO3 0.021 M/h 3.9 Mn= 0 Mn= 0.6
(3.67%)
LaMnO3 0.083 3.9 Mn= 0 Mn= 88
(2.57%)
High mass
catalyst
LnFeO3 0.083 3.9 Fe=0 Fe= 0.03
(88%)
LnFeO3 0.083 3.9 Fe=0 Fe= 0.03
(48%)
LnFeO3 0.006 M/h 3.9 Fe=0 Fe= 0.03
(88%)

The data (Table 11) shows a small dissolution of the metal on the
perovskite after acetic acid oxidation for all the catalysts, except for the test
performed on LaMnO3 (2.57%) with high mass catalyst (Mn=88 ppm).
However, the use of Fe-based perovskites could be desiderable.

121
IX Heterogeneous photo-Fenton:
reaction mechanism hypothesis

In the absence of the catalyst and acetic acid, UV light induces


homogeneous H2O2 decomposition by the following reactions (eqs. 20-23)
(Figure 102):

H 2 O2 + hν → 2OH • (20)

OH • + H 2 O2 → HO2 • + H 2 O (21)

HOO • + H 2 O2 → HO • + H 2 O + O2 (22)

HO2 • + HO2 • → H 2 O2 + O2 (23)


Chapter IX

O2(g)

H 2O2 → 2HO

Figure 102. Photolysis of hydrogen peroxide.


In the absence of the UV light and acetic acid, for the system
H2O2/catalyst, H2O2 decomposition occurred according the following
simplified scheme (Figure 103) (eqs. 24-25):

H 2 O2 (l ) → H 2 O2 (ads ) (24)

1
H 2 O2 (ads ) → H 2 O(l ) + O2 ( g ) (25)
2

124
Heterogeneous photo-Fenton: reaction mechanism hypothesis

O2(g)

H2O2(l)

O2(g)

H2O2ads

Figure 103. Catalytic decomposition of H2O2.


With the simultaneous presence of the catalyst and acetic acid (but in
absence of UV light), homogeneous H2O2 decomposition was inhibited,
because of competitive adsorption of CH3COOH that became prevalent on
catalyst surface (eq. 26). The catalyst is able to initiate the reaction, but both
reactants and products seem to be anchored on the surface.

CH 3 COOH (l ) → CH 3COOH (ads ) (26)

Photo-Fenton oxidation can occur by reaction between OH. UV-


generated and surface adsorbed CH3COOH/oxidation products, regenerating
the active sites. On the basis of these observations, there is a synergic effect
between UV light and the catalyst. In fact, hydroxyl radicals generated by
H2O2 decomposition (activated by UV light) can react with acetic acid in the
liquid phase and on the catalyst surface leading to complete mineralization
of the hydrocarbon (Figure 104) through the probable formation of

125
Chapter IX

intermediate radicals ( R • ) generated by the reaction between acetic acid


and hydroxyl radicals (eqs. 27-32).

H 2 O2 + hν → 2OH • (27)

OH • + H 2 O2 → HO2 • + H 2 O (28)

HOO • + H 2 O2 → HO • + H 2 O + O2 (29)

HO2 • + HO2 • → H 2 O2 + O2 (30)

CH 3 COOH (l ) → CH 3COOH (ads) (31)

CH 3COOH (ads ) + OH • → R• → CO2 (32)

The effect of step dosage of H2O2 is carried out in order to limit the UV
induced decomposition of H2O2, which subtracts and scavenges OH..

126
Heterogeneous photo-Fenton: reaction mechanism hypothesis

O2(g) CO2(g)

1
H 2O2 (l ) → H 2O(l ) + O2 ( g )
2

H2O2 →2HO
H2O2(l
CxHyOz(l )
O2(g)

H2O2a CxHyOz(ad s)
CO2(g)

Figure 104. Illustration of the photo-Fenton process.

127
X Experimental results: photo-
Fenton oxidation of alcohols on
LaMeO3

X.1 Photolysis

X.1.1 Photolysis of ethanol

In Figure 105 it is shown, that after 4 hours, in the photolysis of ethanol


with hydrogen peroxide (H2O2/C2H5OH= 2) about 69% of H2O2 is
converted, when TOC removal was about 47%.
Chapter X

TOC removal, % H2O2 conversion, %

100 100
90 90
80 80

H2O2 conversion, %
TOC removal, %

70 70
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 0,5 1 1,5 2 2,5 3 3,5 4

t, h

Figure 105. Photolysis of ethanol. Experimental conditions: V tot.: 100 ml;


H2O2/C2H5OH= 2; C0H2O2= 0.042 mol/l; C0C2H5OH= 0.021; P= 1 atm;
T=25°C; pH=6.5.

X.1.2 Photolysis of methanol

In Figure 106 it is shown, that after 3.5 hours, in the photolysis of


methanol with hydrogen peroxide (H2O2/CH3OH= 1) about 50% of H2O2 is
converted, when TOC removal is about 40%.

TOC removal, % H2O2 conversion, %


100 100
90 90
H2O2 conversion, %

80 80
TOC removal, %

70 70
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 0,5 1 1,5 2 2,5 3 3,5 4
t, h

Figure 106. Photolysis of methanol. Experimental conditions: V tot.: 100


ml; H2O2/CH3OH= 1; C0H2O2= 0.042 mol/l; C0CH3OH= 0.021 mol/l; P= 1
atm; T=25°C; pH=5.5.

130
Experimental results: photo-Fenton oxidation of alcohols on LaMeO3

X.2 Catalytic photo-Fenton oxidation of ethanol on LaMnO3

(3.67%)

In Figure 107 it is shown, that after 5 hours, in catalytic photo-Fenton


oxidation of ethanol on LaMnO3 (3.67%) with the hydrogen peroxide
(H2O2/C2H5OH= 1) there is similar TOC removal with respect to the
photolysis; particularly, about 100% of H2O2 is converted, when TOC
removal is about 50%.

TOC removal, % H2O2 conversion, %


100 100

90 90

80 80

H2O2 conversion, %
TOC removal, %

70 70

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 0,5 1 1,5 2 2,5 3 3,5 4 4,5 5
t, h

Figure 107. Catalytic photo-Fenton oxidation of ethanol on LaMnO3


(3.67%). Experimental conditions: V tot.: 100 ml; H2O2/C2H5OH= 2;
C0H2O2= 0.042 mol/l; C0C2H5OH= 0.021; P= 1 atm; T=25°C; pH=6.5.

X.3 Catalytic photo-Fenton oxidation of methanol on LaMnO3

(3.67%)

In Figure 108 it is shown, that after 4 hours, in the catalytic photo-Fenton


oxidation of the methanol on LaMnO3 (3.67%) with the hydrogen peroxide
(H2O2/CH3OH= 1) there is higher TOC removal with respect to the
photolysis; particularly, about 74% of H2O2 is converted, when TOC
removal is about 47%.

131
Chapter X

TOC removal, % H2O2 conversion, %


100 100

90 90

80 80

H2O2 conversion, %
TOC removal, %

70 70

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 0,5 1 1,5 2 2,5 3 3,5 4
t, h

Figure 108. Catalytic photo-Fenton oxidation of methanol on LaMnO3


(3.67%). Experimental conditions: V tot.: 100 ml; H2O2/CH3OH= 1;
C0H2O2= 0.042 mol/l; C0CH3OH= 0.021 mol/l ; P= 1 atm; T=25°C; pH=5.5.

132
XI Experimental results: photo-
Fenton oxidation of synthetic
winery wastewater on LaMeO3

Wine distilleries produce large volumes of wastewaters, called


“vinasses”, the composition of which varies widely according to the raw
material distilled: wine, pressed grapes, etc. In general, all of them have an
acidic pH and a high organic substrate content with chemical oxygen
demand in the range 10±40 g/l. Usually these effluents are eliminated
through public sewerages, and therefore this represents a large-scale
environmental problem, due to the pollution that they introduce in surface
and underground waters.
Although little attention has been paid in the past to this problem, at the
present moment and as a consequence of the potential hazards caused by this
waste, many countries have limited its discharge and tried to develop
alternative technologies to reduce its toxic effect by degrading the main
organic substances present. Among these technologies, biological processes
have been recognized as effective methods for the degradation of
wastewaters with a high organic pollutant load, such as those coming from
wine distilleries. As a result, aerobic treatment systems, such as aerated
lagoons or activated sludge plants, are used to remove the contamination
generated by these residues.
However, several problems have been encountered during aerobic
treatments which are linked to the high toxicity of effluents. They lead to the
partial inhibition of biodegradation, because some microorganisms are
particularly sensitive to the organic compounds present, especially phenolic
compounds. Therefore, other treatments, such as chemical oxidation have
recently been investigated successfully for the purification of wastewaters
with these type of phenolic substances. Among these procedures, photo-
Fenton processes have increasingly been used because hydrogen peroxide
has many of the oxidizing properties desirable for water treatments: it is a
powerful oxidant that degrades a large number of organic compounds in
general and specifically phenolic compounds.
Chapter XI

The conditions applied in each experiment were modified using different


H2O2/TOCinitial ratio (M/M) and the following conditions:
• Organic matter concentration: 500 mg C/l (measured as TOC).
• H2O2 concentration: 0.042 and 0.084 M, corresponding to
H2O2/TOCinitial ratio (M/M) = 1 and 2 respectively.
Different oxidation systems have been investigated using synthetic
samples, which were representative of real winery wastewaters. Similar
properties were achieved by diluting commercial red wine (“Chianti” or
local wine not containing sulphites) with ultra-pure water, obtaining
approximately the amount of the organic matter equal to 500 mg C/l
(measured as TOC).

134
Experimental results: photo-Fenton oxidation of synthetic winery wastewater on LaMeO3

XI.1 Photolysis of synthetic winery wastewaters (red wine)

Figure 109 shows photolysis of synthetic winery wastewaters with


H2O2/TOCwine= 1 obtained by diluting commercial red wine. Total organic
removal is about 12% when H2O2 conversion is 48%.

TOC removal, % H2O2 conversion, %


100 100
90 90
80 80

H2O2 conversion, %
TOC removal, %

70 70
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 0,5 1 1,5 2 2,5 3 3,5 4
t, h

Figure 109. Photolysis of synthetic winery wastewaters obtained by diluting


commercial red wine. Experimental conditions: V tot.: 100 ml;
H2O2/TOCwine= 1; C0H2O2= 0.042 mol/l; P= 1 atm; T=25°C; pH=4.2.
The higher concentration of H2O2 (H2O2/TOCwine= 2) slightly increased
total organic removal; particularly, total organic removal is about 23%, when
H2O2 conversion is 22% (Figure 110).

135
Chapter XI

TOC removal, % H2O2 conversion, %


100 100

90 90

80 80

H2O2 conversion, %
TOC removal, %

70 70

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 0,5 1 1,5 2 2,5 3 3,5 4
t, h

Figure 110. Photolysis of synthetic winery wastewaters obtained by diluting


commercial red wine. Experimental conditions: V tot.: 100 ml;
H2O2/TOCwine= 2; C0H2O2= 0.042 mol/l; P= 1 atm; T=25°C; pH=4.2.

136
Experimental results: photo-Fenton oxidation of synthetic winery wastewater on LaMeO3

XI.2 Photolysis of synthetic winery wastewaters (red wine not

containing sulphites)

Figure 111 shows photolysis of synthetic winery wastewaters with


H2O2/TOCwine= 1 obtained by diluting commercial red wine not containing
sulphites. Total organic removal is about 25% when H2O2 conversion is
47%.

TOC removal, % H2O2 conversion, %


100 100

90 90

80 80

H2O2 conversion, %
TOC removal, %

70 70

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 0,5 1 1,5 2 2,5 3
t, h

Figure 111. Photolysis of synthetic winery wastewaters obtained by diluting


commercial red wine not containing sulphites. Experimental conditions: V
tot.: 100 ml; H2O2/TOCwine= 1; C0H2O2= 0.042 mol/l; P= 1 atm; T=25°C;
pH=4.2.

137
Chapter XI

Figure 112 shows the photolysis of synthetic winery wastewaters with


H2O2/TOCwine= 2 obtained by diluting commercial red wine not containing
sulphites. Total organic removal is about 48% when H2O2 conversion is
63%.

TOC removal, % H2O2 conversion, %

100 100

90 90

80 80

H2O2 conversion, %
TOC removal, %

70 70

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 0,5 1 1,5 2 2,5 3 3,5 4
t, h

Figure 112. Photolysis of synthetic winery wastewaters obtained by diluting


commercial red wine not containing sulphites. Experimental conditions: V
tot.: 100 ml; H2O2/TOCwine= 2; C0H2O2= 0.084 mol/l; P= 1 atm; T=25°C;
pH=4.2.

138
Experimental results: photo-Fenton oxidation of synthetic winery wastewater on LaMeO3

XI.3 Catalytic photo-Fenton oxidation of synthetic winery

wastewaters (red wine) on LaMnO3 (3.67%)

In Figure 113 it is showed that after 4 hours, in catalytic photo-Fenton


oxidation of synthetic winery wastewaters obtained by diluting commercial
red wine on LaMnO3 (3.67%) with hydrogen peroxide (H2O2/TOCwine = 1)
there is higher TOC removal with respect to photolysis; particularly, about
26% of H2O2 is converted, when TOC removal is about 17%.

TOC removal, % H2O2 conversion, %


100 100
90 90
80 80

H2O2 conversion, %
TOC removal, %

70 70
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 0,5 1 1,5 2 2,5 3 3,5 4
t, h

Figure 113. Catalytic photo-Fenton oxidation of synthetic winery


wastewaters obtained by diluting commercial red wine on LaMnO3 (3.67%).
Experimental conditions: V tot.: 100 ml; H2O2/TOCwine= 1; C0H2O2= 0.042
mol/l; P= 1 atm; T=25°C; pH=4.2.
The higher concentration of H2O2 (H2O2/TOCwine= 2) slightly increased
total organic removal; particularly, total organic removal is about 20%, when
H2O2 conversion is 33% (Figure 114).

139
Chapter XI

TOC removal, % H2O2 conversion, %


100 100
90 90

H2O2 conversion, %
80 80
TOC removal, %
70 70
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 0,5 1 1,5 2 2,5 3 3,5 4
t, h

Figure 114. Catalytic photo-Fenton oxidation of synthetic winery


wastewaters obtained by diluting commercial red wine on LaMnO3 (3.67%).
Experimental conditions: V tot.: 100 ml; H2O2/TOCwine= 2; C0H2O2= 0.042
mol/l; P= 1 atm; T=25°C; pH=4.2.

140
Experimental results: photo-Fenton oxidation of synthetic winery wastewater on LaMeO3

XI.4 Catalytic photo-Fenton oxidation of synthetic winery

wastewaters (local red wine not containing sulphites) on

LaMnO3 (3.67%)

In Figure 115 it is showed that after 3 hours, in catalytic photo-Fenton


oxidation of synthetic winery wastewaters obtained by diluting local red
wine, not containing sulphites, on LaMnO3 (3.67%) with hydrogen peroxide
(H2O2/TOCwine= 1) about 35% of H2O2 is converted, when TOC removal is
about 29%.

TOC rem oval, % H2O2 conversion, %


10 0 10 0
90 90
80 80

H2O2 conversion, %
TOC removal, %

70 70
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 0 ,5 1 1, 5 2 2 ,5 3 3 ,5 4
t, h

Figure 115. Catalytic photo-Fenton oxidation of synthetic winery


wastewaters obtained by diluting local red wine on LaMnO3 (3.67%).
Experimental conditions: V tot.: 100 ml; H2O2/TOCwine= 1; C0H2O2= 0.042
mol/l; P= 1 atm; T=25°C; pH=4.2.

In Figure 116 it is showed that after 3 hours, in catalytic photo-Fenton


oxidation of synthetic winery wastewaters obtained by diluting the local red
wine, not containing sulphites, on LaMnO3 (3.67%) with the hydrogen
peroxide (H2O2/TOCwine= 2) about 79% of H2O2 is converted, when TOC
removal is about 51%.

141
Chapter XI

TOC removal, % H2O2 conversion, %


100 100
90 90

H2O2 conversion, %
TOC removal, % 80 80
70 70
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 1 2 3
t, h

Figure 116. Catalytic photo-Fenton oxidation of synthetic winery


wastewaters obtained by diluting local red wine on LaMnO3 (3.67%).
Experimental conditions: V tot.: 100 ml; H2O2/TOCwine= 2; C0H2O2= 0.084
mol/l; P= 1 atm; T=25°C; pH=4.2.

XI.5 Catalytic photo-Fenton oxidation of the synthetic winery

wastewaters (red wine local not containing sulphites) on

LnFeO3 (48%)

In Figure 117 it is showed, that after 3 hours, in catalytic photo-Fenton


oxidation of synthetic winery wastewaters obtained by diluting the local red
wine, not containing sulphites, on LnFeO3 (48%) with hydrogen peroxide
(H2O2/TOCwine= 1) about 50% of H2O2 is converted, when TOC removal is
about 30%.

142
Experimental results: photo-Fenton oxidation of synthetic winery wastewater on LaMeO3

TOC removal, % H2O2 conversion, %


100 100

90 90

80 80

H2O2 conversion, %
70 70
TOC removal, %

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 0,5 1 1,5 2 2,5 3
t, h

Figure 117. Catalytic photo-Fenton oxidation of synthetic winery


wastewaters obtained by diluting local red wine on LnFeO3 (48%).
Experimental conditions: V tot.: 100 ml; H2O2/TOCwine= 1; C0H2O2= 0.042
mol/l; P= 1 atm; T=25°C; pH=4.2.

143
Chapter XI

XI.6 Effect of dosage of H2O2 (red wine local not containing

sulphites)

In the photo-Fenton process with LaMnO3 (3.67%) (Figure 118), the


addition of H2O2 equal to 0.009 M/h increases total organic removal from
43% (H2O2/TOCwine =2) to 50%.
TOC removal LaMnO3 (3.67%) with H2O2 added, % H2O2, ppm

100
1400
90

80 1200
TOC removal, %

70
1000

H2O2, ppm
60
800
50

40 600

30
400
20
200
10

0 0
0 1 2 3 4 5 6 7

t, h

Figure 118. Effect of dosage of H2O2 on the catalytic activity of LaMnO3


(3.67%). Experimental conditions: V tot.: 100 ml; mcatalyst= 4.9 g; TOC0wine=
500 mg/l; C0H2O2= 0.006 mol/l; CH2O2/t= 0.009 M/h; P= 1 atm; T=25°C;
pH=4.2.

Table 12 shows a comparison of hydrogen peroxide consumption of the


photo-Fenton of LaMnO3 (3.67%) with step dosage of H2O2 with respect to
the photo/LaMnO3 system that starts with H2O2/TOCwine=2. There is lower
hydrogen peroxide consumption in the presence of dosage of hydrogen
peroxide with respect to the photo/LaMnO3 system without dosage.
Particularly, a higher final total organic carbon removal (49%) is noted in the
presence of dosage of hydrogen peroxide with respect to the photo/LaMnO3
system with initial molar ratio H2O2/ TOCwine=2 (43 %). Moreover, a smaller
specific consumption defined by molar ratio H2O2/TOCwine is noted.
Particularly, it varies in the 0.5 mol/mol (0.6 gH2O2/gC) 3.9 mol/mol (5.6
gH2O2/gC) range in the test with dosage, and in the 5.6 mol/mol (8.0 gH2O2/gC)
5.8 mol/mol (8.2 gH2O2/gC) range in the test without dosage.

144
Experimental results: photo-Fenton oxidation of synthetic winery wastewater on LaMeO3

Table 12. Comparison of hydrogen peroxide consumption of photo-Fenton


of LaMnO3 (3.67%) with dosage of H2O2 with respect to the photo/LaMnO3
system with H2O2/ TOCwine =2.

TOC Dosage Dosage No dosage No Dosage


removal, H2O2 H2O2 cons., H2O2 cons., H2O2 cons.,
% consumption, gH2O2/gc ppm gH2O2/gc
ppm
15 48 0.6 600 8.0

30 453 3.0 1144 7.6

43 1201 5.6 1773 8.2

In the photo-Fenton process with LnFeO3 (48%) (Figure 119), the


addition of H2O2 equal to 0.012 M/h increases total organic removal from
30% (H2O2/TOCwine =1) to 70%.

TOC removal LnFeO3 (48%) with H2O2 added, % H2O2, ppm


100
1400
90

80 1200
TOC removal, %

70
1000
H2O2, ppm

60
800
50

40 600

30
400
20
200
10

0 0
0 1 2 3 4 5 6 7 8
t, h

Figure 119. Effect of dosage of H2O2 on the catalytic activity of LnFeO3


(48%). Experimental conditions: V tot.: 100 ml; mcatalyst= 14 g; TOC0wine=
500 mg/l; C0H2O2= 0.006 mol/l; CH2O2/t= 0.012 M/h; P= 1 atm; T=25°C;
pH=4.2.
Table 13 shows a comparison of hydrogen peroxide consumption of the
photo-Fenton of LnFeO3 (48%) with step dosage of H2O2 with respect to the
photo/LnFeO3 system that starts with H2O2/TOCwine=1. There is higher
hydrogen peroxide consumption in the presence of dosage of hydrogen
peroxide with respect to the photo/LnFeO3 system without dosage.

145
Chapter XI

Nevertheless, a higher final total organic carbon removal (68%) is noted in


presence of the dosage of hydrogen peroxide with respect to the
photo/LaMnO3 system with initial molar ratio H2O2/ TOCwine=1 (30 %).
Moreover, a smaller specific consumption defined by molar ratio
H2O2/TOCwine is noted; more specifically it varied in the 1.3 mol/mol (1.8
gH2O2/gC) 5.6 mol/mol (7.9 gH2O2/gC) range in the test with dosage, while it
varied in the 2.0 mol/mol (2.9 gH2O2/gC) 3.3 mol/mol (4.8 gH2O2/gC) range in
the test without dosage.

Table 13. Comparison of hydrogen peroxide consumption of the photo-


Fenton of LnFeO3 (48%) with dosage of H2O2 with respect to the
photo/LnFeO3 system with H2O2/ TOCwine =1.

TOC Dosage Dosage No dosage No Dosage


removal, H2O2 H2O2 cons., H2O2 cons., H2O2 cons.,
% consumption, gH2O2/gc ppm gH2O2/gc
ppm
10 91 1.8 143 2.9

30 655 4.4 715 4.8

68 2701 7.9 - -

XI.7 Leaching test

The data of the dissolution (Table 14) show a small dissolution of the
metal on the perovskite after synthetic winery wastewater oxidation for all
the catalysts.

146
Experimental results: photo-Fenton oxidation of synthetic winery wastewater on LaMeO3

Table 14. Metal ion analysis of the some catalysts used for the catalytic
photo-Fenton reaction of synthetic winery wastewater.
Catalyst [H202]= pH Metal Metal
mol/l iont=0 ionfinal time
(ppm) (ppm)
LaMnO3 0.084 4.2 Mn= 0 Mn= 0.22
(3.67%)
LaMnO3 0.009 M/h 4.2 Mn= 0 Mn= 0.12
(3.67%)
LnFeO3 0.084 4.2 Fe=0 Fe= 0.03
(48%)
LnFeO3 0.006 M/h 4.2 Fe=0 Fe= 0.03
(48%)

Mn and Fe final concentration resulted lower than legal emissions limits


(2 ppm).

147
XII Conclusions

Heterogeneous Fenton catalytic oxidation resulted a promising


technology for treating aqueous solutions containing not biodegradable
organic substances.
The difference in TOC removal in homogeneous and heterogeneous
Fenton-type oxidation greatly encourages the use and the study of the
heterogeneous catalytic system.
Heterogeneous Fenton catalytic oxidation is effective in the treatment of
real tannery wastewaters.
Higher performances were obtained by adding UV irradiation to Fenton
system.
The use of a heterogeneous structured catalyst in the photo-Fenton
reaction greatly improves TOC removal and leads to better use of H2O2,
leading to enlarge pH range of operation, without formation of sludge or
enhancement in metal leaching from the solid catalyst. Particularly, LaMnO3
and LaFeO3 resulted the best catalysts for this process.
It has been found that, from the values of TOC removal and carbon
dioxide concentration formed, the total carbon mass balance was closed to
100%, indicating that the mineralization of the acetic acid is complete after
oxidation treatment.
In photo-Fenton processes, the efficiency depends from optimisation of
H2O2 concentration level, that can be achieved by continuous dosage of
H2O2 during reaction time, since TOC removal is dependent by H2O2
utilisation for oxidation with respect to its decomposition to oxygen.
It has also been found that the photocatalytic advanced process based on
H2O2 is an appropriate purification treatment of synthetic winery
wastewaters, by combining LnFeO3 and LaMnO3 monoliths with step dosage
of H2O2. In this conditions, TOC removal higher than 65 % could be reached
in 7 hours, without significant metal leaching.
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