The document discusses the use of metal/support catalysts for ozonation reactions. It examines how various catalysts like Pd/SiO2 and Ru/CeO2 decompose ozone and finds that 3% Pd/SiO2 and impregnated Ru/CeO2 are the most effective. The document also looks at how factors like catalyst preparation method, support material, metal loading amount and pH level can influence the ozonation rate.

1. Ozonation catalysed by Me/support catalysts.
Liudmyla Masliuk
11.03.2014
Liudmyla Masliuk (SERP-Chem M2) Ozonation catalysed by Me/support catalysts. 11.03.2014 1 / 15

2. Introduction
Does the catalyst decompose ozone?
Is ozonation with catalyst more efficient than without?
Liudmyla Masliuk (SERP-Chem M2) Ozonation catalysed by Me/support catalysts. 11.03.2014 2 / 15

3. Various catalysts
Article Effective catalysts for decomposition of aqueous ozone
Authors Jianjun Lin , Akimasa Kawai, Tsuyoshi Nakajima
Journal Applied Catalysis B: Environmental 39 (2002) 157 − 165
Catalyst Pt, Pd, Ag, Ru, Rh, Ir, Ni, Cd, Mn, Fe, Cu, Zn, Zr, Co, Y,
Mo, Ti and Au
Support AC, zeolite (HY and mordenite), Al2O3, SiO2 ,
SiO2 · Al2O3 and TiO2
Preparation impregnation
Pollutant no
Details Al2O3 stable against ozone, Pt/SiO2 gives best rate
Result 3% Pd/SiO2 the most effective
Liudmyla Masliuk (SERP-Chem M2) Ozonation catalysed by Me/support catalysts. 11.03.2014 3 / 15

4. Few more details
Catalysts
Support, impregnated to
respective salt solution was
dried for 1 night at 383 K and
than calcined for 3 h at 773 K
Liudmyla Masliuk (SERP-Chem M2) Ozonation catalysed by Me/support catalysts. 11.03.2014 4 / 15

5. Few more details
Catalysts
Support, impregnated to
respective salt solution was
dried for 1 night at 383 K and
than calcined for 3 h at 773 K
Ozone
Water, saturated with ozone
was pumped through a catalytic
bed and ozone level was
measured before and after
flowing through.
Liudmyla Masliuk (SERP-Chem M2) Ozonation catalysed by Me/support catalysts. 11.03.2014 4 / 15

6. Few more details
Catalysts
Support, impregnated to
respective salt solution was
dried for 1 night at 383 K and
than calcined for 3 h at 773 K
Ozone
Water, saturated with ozone
was pumped through a catalytic
bed and ozone level was
measured before and after
flowing through.
Supports
Ozone decomposition rate for
some supports
Support Rate (mgO3
min−1
g−1
cat )
AC 0.25
Zeolite (mordenite) 0.02
Al2O3, SiO2 0.01
others 0
Liudmyla Masliuk (SERP-Chem M2) Ozonation catalysed by Me/support catalysts. 11.03.2014 4 / 15

7. Main results
Liudmyla Masliuk (SERP-Chem M2) Ozonation catalysed by Me/support catalysts. 11.03.2014 5 / 15

8. Pd and Pt
Surface
Catalyst Specific surface Rate,
area, m2
/g mgO3
/min/gcat
Pd/SiO2 206 0.77
Pd/SiO2 · Al2O3 221 0.54
Pd/Al2O3 139 0.39
Pd/TiO2 34 0.35
Liudmyla Masliuk (SERP-Chem M2) Ozonation catalysed by Me/support catalysts. 11.03.2014 6 / 15

9. Pd and Pt
Surface
Catalyst Specific surface Rate,
area, m2
/g mgO3
/min/gcat
Pd/SiO2 206 0.77
Pd/SiO2 · Al2O3 221 0.54
Pd/Al2O3 139 0.39
Pd/TiO2 34 0.35
Amount
Catalyst Amount, Rate,
% mgO3
/min/gcat
Pd/SiO2 0.5 0.68
1 0.84
3 0.96
5 0.77
Pd/Al2O3 0.5 0.42
1 0.46
3 0.50
5 0.40
Liudmyla Masliuk (SERP-Chem M2) Ozonation catalysed by Me/support catalysts. 11.03.2014 6 / 15

10. Pd and Pt
Surface
Catalyst Specific surface Rate,
area, m2
/g mgO3
/min/gcat
Pd/SiO2 206 0.77
Pd/SiO2 · Al2O3 221 0.54
Pd/Al2O3 139 0.39
Pd/TiO2 34 0.35
Amount
Catalyst Amount, Rate,
% mgO3
/min/gcat
Pd/SiO2 0.5 0.68
1 0.84
3 0.96
5 0.77
Pd/Al2O3 0.5 0.42
1 0.46
3 0.50
5 0.40
Liudmyla Masliuk (SERP-Chem M2) Ozonation catalysed by Me/support catalysts. 11.03.2014 6 / 15

11. Ru/CeO2
Article Relationship between the structure of Ru/CeO2 catalysts
and their activity in the catalytic ozonation of succinic acid
aqueous solutions
Authors F. Delanoe, B. Acedo, N. Karpel Vel Leitner, B. Legube
Journal Applied Catalysis B: Environmental 29 (2001) 315 − 325
Preparation impregnation or acid exchange
Pollutant succinic acid
Result impregnated catalyst gives better efficiency
Liudmyla Masliuk (SERP-Chem M2) Ozonation catalysed by Me/support catalysts. 11.03.2014 7 / 15

12. Preparation
2% Ru/CeO2
Impregnation
Support impregnated into
Ru(NH3)6Cl3 solution for 20 h,
dried at 323K, than reduced
under hydrogen flow for 20 h at
623K
≥ 1.4%Ru
Liudmyla Masliuk (SERP-Chem M2) Ozonation catalysed by Me/support catalysts. 11.03.2014 8 / 15

13. Preparation
2% Ru/CeO2
Impregnation
Support impregnated into
Ru(NH3)6Cl3 solution for 20 h,
dried at 323K, than reduced
under hydrogen flow for 20 h at
623K
≥ 1.4%Ru
Acid exchange
RuCl3 solution at pH 2.4 in HCl
was stirred with CeO2 powder
for 20h and treated in the same
way after filtration and drying
≥ 1.1%Ru
Liudmyla Masliuk (SERP-Chem M2) Ozonation catalysed by Me/support catalysts. 11.03.2014 8 / 15

14. Procedure
O3 was introduced continuously to aqueous solution of succinic
acid in a presence of powdered catalyst
2 sets of conditions: SA 1 mmol/l, catalyst 0.8 g/l and SA 5
mmol/l, catalyst 3.2 g/l
4 experiments: 0.5 mmol/l SA for impregnated and 0.3 mmol/l
for acid exchanged catalyst
SA removed by ozonation at this conditions (pH = 3.4) < 4%
SA absorbed < 10%
Liudmyla Masliuk (SERP-Chem M2) Ozonation catalysed by Me/support catalysts. 11.03.2014 9 / 15

15. Concentration
Low concentration High concentration
Liudmyla Masliuk (SERP-Chem M2) Ozonation catalysed by Me/support catalysts. 11.03.2014 10 / 15

16. Multiple treatment
Initial rates of SA ( ) and TOC ( ) conversion for four successive
catalytic ozonation experiments; Fig. a: I catalyst; Fig. b: AE catalyst.
Liudmyla Masliuk (SERP-Chem M2) Ozonation catalysed by Me/support catalysts. 11.03.2014 11 / 15

17. Ru/CeO2
Article Catalytic ozonation of chlorinated carboxylic acids with
Ru/CeO2 − TiO2 catalyst in the aqueous system
Authors Hongxiang Fu, Nathalie Karpel Vel Leitner and Bernard
Legube
Journal New J. Chem., 2002, 26, 1662 − 1666
Preparation impregnation or acid exchange
Pollutant Chloroacetic acid (CAA) and chlorosuccinic acid (CSA)
Liudmyla Masliuk (SERP-Chem M2) Ozonation catalysed by Me/support catalysts. 11.03.2014 12 / 15

18. CAA. pH control
Room temperature, catalyst amount: 0.8 gL−1, introduced O3 flow
rate: 1275 ± 25 mgh−1
pH influence
pKa of CAA 2.86. CAA initial
concentration: 0.65 mM.
Liudmyla Masliuk (SERP-Chem M2) Ozonation catalysed by Me/support catalysts. 11.03.2014 13 / 15

19. CAA. pH control
Room temperature, catalyst amount: 0.8 gL−1, introduced O3 flow
rate: 1275 ± 25 mgh−1
pH influence
pKa of CAA 2.86. CAA initial
concentration: 0.65 mM.
pH adjustment
Initial pH: 3.1, CAA initial
concentration: 2.0 mM.
Liudmyla Masliuk (SERP-Chem M2) Ozonation catalysed by Me/support catalysts. 11.03.2014 13 / 15

20. Ru/Al2O3 + Ce
Catalytic activity of cerium-doped Ru/Al2O3 during ozonation of
dimethyl phthalate
Yunrui ZHOU, Wanpeng ZHU, Xun CHEN Sci. Engin. China 2008,
2(3): 354 − 357
TOC removal rate
catalyst Chet CO Chom Cabs
Ru-Ce 35.4 24.1 33.1 7.40
Ce-Ru 42.6 24.9 24.8 7.65
mixture of Ce and Ru 45.8 26.4 19.7 8.10
Ru 50.4 38.0 − 11.6
Liudmyla Masliuk (SERP-Chem M2) Ozonation catalysed by Me/support catalysts. 11.03.2014 14 / 15

21. Ce amount influence
Ce load
Liudmyla Masliuk (SERP-Chem M2) Ozonation catalysed by Me/support catalysts. 11.03.2014 15 / 15

22. Ce amount influence
Ce load Ce ions influence
Liudmyla Masliuk (SERP-Chem M2) Ozonation catalysed by Me/support catalysts. 11.03.2014 15 / 15