Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Sameer Damle
Department of Chemical Engineering University of Pittsburgh
Side reactions:
Exhaust NH3 oxidation (detrimental) NOx containing NO oxidation (desirable) NH4NO3 formation
Literature survey
SCR over Vanadia-based catalyst well studied in literature Langmuir-Hinshelwood and Eley-Rideal mechanisms proposed for SCR [1,2] Vanadia based catalyst gives sluggish performance at low temperatures [3] Fe and Cu based catalyst give better activity at low temperatures and are cheaper [4,5] Few detailed kinetic studies on Fe-based zeolite catalyst [6,7]
Outline
Objectives of the paper Experimental methodology Results Conclusion Assessment of paper
Experimental Methodology
commercial sample (XRD, ICP, SEM, EDS, BET) Catalyst testing done in bench scale reactor
Reactor
Quartz tube reactor Monolith catalyst Tube furnace
Analytical System
Data Acquisition
Temperature:: 100 to 500o C Pressure: 880 mm of Hg Argon used as balance gas Catalyst dimensions varied to obtain high space velocity (GHSV) for differential operation
8
qA =
DH K A = K A0 exp RT
Surface coverage against concentration Langmuir isotherm
12
13
Oxidation of Ammonia
For zeolite based catalyst, NH3 oxidation reaction is:
As water does not hinder NH3 uptake, this suggests water inhibits oxygen adsorption
15
Oxidation of NO
NO oxidizes to NO2 in presence of O2 NO2 formation is desirable in SCR system as NO2 is more reactive with NH3 than NO put fast scr here : faster
Steady state NO oxidation carried out at different temperatures Conversion of NO found to be maximum at 350o C Conversion found to be equilibrium limited above 350o C Results from commercial and in-house catalyst found to be comparable
Outlet concentration of NO during NO oxidation with O2 at different temperatures
Solid lines- commercial catalyst Dash lines- in-house catalyst 16
O2
NO2
~ 0.5
~ -0.5
Activation energy for reaction calculated: Eact=39 kJ/mol Langmuir-Hinshelwood mechanism proposed
NO adsorption Oxygen adsorption Surface reaction NO2 desorption Hindrance by water
19
The mechanism takes into account the inhibition effects of H2O and NO2 Orders predicted by rate expression are similar to experimental observations
20
21
22
a b g
E
23
24
Washcoat
B
22% 1 cm
(A) (B)
i.e.
kept constant
Comparison of NO conversion during SCR over sample A and B
26
Pore diffusion changes the apparent reaction rate Apparent activation energy of SCR reaction was calculated at higher temperatures to better understand the mass transfer limitations. . Temperature range Activation energy (kJ/mol)
150-300 350-500 42 24
Reduction in apparent activation energy by factor 2 confirms washcoat diffusion limitations at high temperatures
http://www.pitt.edu/~gveser/ChE2201/classnotes1.html
Paper suggests that washcoat diffusion should be considered while modeling the reaction at higher temperatures.
27
28
Both reactions improve when the Fe content in the catalyst is increased This suggests that NO oxidation is likely the rate determining step for standard SCR
29
Effect of H2O
No effect
Inhibition
Inhibition
This shows that NH3 adsorbs on acidic sites (S2), while oxidation reaction takes place on other sites (S1) Blocking of active sites by NH3 is attributed to NH3 spillover from S2 to S1 Reaction mechanism is proposed assuming NO oxidation as the RDS and considering two different active sites (S1 and S2)
30
31
Surface coverage of NO
Reaction between gas phase NO and adsorbed O Eley-Rideal mechanism:
32
Transient experiments
33
34
Effect of increasing temperature: Amount of NH3 adsorbed SCR reaction duration Net amount of N2 produced Decreased Decreased Decreased
Peak N2 concentration
Increased
Data from transient studies supports the steady state experimental data
35
Conclusion
Systematic study performed to understand the reaction system (NO + NH3 +O2) Differential kinetics derived for SCR reaction comparable to values reported in literature Performance of in-house catalyst comparable to the commercial catalyst showing the catalyst synthesis ability Dual-site (S1 and S2) Langmuir-Hinshelwood kinetic model proposed in agreement with the experimental findings Washcoat mass transfer limitations at higher temperatures pointed out
36
37
38
39
Thank you
41
References
1. G. Busca, L. Lietti, G. Ramis, F. Berti, Applied Catalysis B: Environmental 18 (1998) 136. H.J. Chae, S.T. Choo, H. Choi, I.S. Nam, H.S. Yang, S.L. Song, Industrial and Engineering Chemistry Research 39 (2000) 11591170. A. Grossale, I. Nova, E. Tronconi, D. Chatterjee, M. Weibel, Journal of Catalysis 256 (2008) 312322. K. Kamasamudram, N.W. Currier, X. Chen, A. Yezerets, Catalysis Today 151 (2010) 212222. K. Kamasamudram, N.W. Currier, T. Szailer, A. Yezerets, SAE Technical Paper 2010-01-1182 (2010). H. Sjovall, R.J. Blint, A. Gopinath, L. Olsson, Industrial and Engineering Chemistry Research 49 (2010) 3952. M. Devadas, O. Krocher, M. Elsener, A. Wokaun, N. Soger, M. Pfeifer, Y. Demel, L. Mussmann, Applied Catalysis B: Environmental 67 (2006) 187196.
42
2.
3. 4. 5. 6. 7.
43
NOx g/hp-hr
EPA 98
EPA 02
EPA 07
EPA 10
0.0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10 0.11 0.12 0.13
Particulate g/hp-hr
45
Fig 5: a)steady state Nox/NO2 outlet concentration ratio at different temperatures b) NO conversion at different NO2/NOx inlet ratio c) plot to find order wrt NO2 for NO oxidation d) NO conversion in presence of water
46
47
Eley-Rideal model: reaction between adsorbed O and gas phase NO to be rate limiting
Both mechanisms correctly predict the experimentally observed order with respect to NO and O2
50
52
53
54
Fig 13: Arrhenius plot for rate of NO conversion against inverse of catalyst temperature
55
Fig 15 (a):Comparison of rate of NO oxidation and standard SCR reaction at different temperatures
56
Fig 15 (b): Outlet NO2 concentration with increasing NH3 concentration in a system containing NO2 and O2
57
Fig 17: Concentrations of N2, NO and NO2 at different temperatures during transient experiments with preadsorbed NH3
58