Selective catalytic reduction of NO with NH3 on iron zeolite catalysts: Steady-state and transient kinetics

Metkar et al., Appl.Catal. B:Environ. 2011.

May 23, 2012

Sameer Damle
Department of Chemical Engineering University of Pittsburgh

Advisor: Dr. Spandan Maiti, Dr. Prashant Kumta

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Background : Selective catalytic reduction (SCR)

Diesel engine emissions: CO2, CO, NOx, Sox, etc Reaction considered: O2 present in excess Standard SCR
NH3 6H 4NH3 + 4NO + 4O2 4N2 + supplyO 2

Side reactions:
Exhaust NH3 oxidation (detrimental) NOx containing NO oxidation (desirable) NH4NO3 formation

System has excess of ONHand H2O 2 3+NO+H2

O+O2 N2+H2O

Diesel engine (lean operation)

http://www.bluecat.ie/FAQ/SCR_Technology_FAQ/What_is_SCR_Technology.html 2

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

Objectives of the paper

Study kinetics of the SCR reaction system on Fe-ZSM-5 catalyst Understand mechanism and selectivity trends of the reaction Comparing the commercial and in-house synthesized catalyst Assess the contribution of mass transfer limitations

Experimental Methodology

Catalyst for reaction

Commercial catalyst: Sud-Chemie (Germany) In-house synthesis of catalyst Ion exchange in ammonium form zeolite + NH 4 H + Na+ Fe2+ / Fe3+
Slurry of zeolite catalyst, -Alumina and water ball milled to make fine suspension Dip-coating Cordierite monolith with the slurry followed by drying Catalyst characterized to compare with

SEM image of washcoated zeolite monolith catalyst (Fe-ZSM-5)

Metkar et al., Chem. Eng. Sci. 2011

commercial sample (XRD, ICP, SEM, EDS, BET) Catalyst testing done in bench scale reactor

Bench-scale reactor setup (PFR)

Gas Supply
Gases: NO, O2 ,NO2, NH3, H2O, Ar Concentration and flow control

Reactor
Quartz tube reactor Monolith catalyst Tube furnace

Analytical System

Data Acquisition

FT-IR spectrometer Mass spectrometer

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
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Results: Kinetics evaluation and kinetic model development

Study of kinetics of SCR reaction system

Adsorption/desorption of NH3 on catalyst 3

Oxidation of NH3 to N2 and NOx (detrimental)

Oxidation of NO to NO2 (desirable)

SCR of NO with NH3

Assess mass transfer limitations Kinetic model development

Study of kinetics of all these individual reactions is necessary

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Ammonia uptake and temperature programmed desorption study

NH3 adsorption studied at different concentrations and temperatures Langmuir type dependence on NH3 concentration observed Average Hads = -115 kJ/mol Water had negligible effect on amount of NH3 adsorbed
K A PA 1+ K A PA

qA =

DH K A = K A0 exp RT
Surface coverage against concentration Langmuir isotherm
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Kinetics of SCR reaction system

Adsorption/desorption of NH3 on catalyst

Oxidation of NH3 to N2 and NOx (detrimental)

Oxidation of NO to NO2 (desirable)

SCR of NO with NH3

Assess mass transfer limitations Kinetic model development

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Oxidation of Ammonia
For zeolite based catalyst, NH3 oxidation reaction is:

Ammonia oxidation is undesirable as less NH3 is available for NO reduction

Oxidation studied over range of temperatures Negligible conversion below 250 oC NH3 and O2 found to have positive order effect Water found to retard the oxidation reaction
Ammonia conversion at different temperatures
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As water does not hinder NH3 uptake, this suggests water inhibits oxygen adsorption

Kinetics of SCR reaction system

Adsorption/desorption of NH3 on catalyst

Oxidation of NH3 to N2 and NOx (detrimental)

Oxidation of NO to NO2 (desirable)

SCR of NO with NH3

Assess mass transfer limitations Kinetic model development

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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

Oxidation of NO (inhibition by NO2)

Effect of NO2 studied at steady state conditions varying the amount of NO2 in the feed Presence of NO2 in the system found to inhibit NO oxidation NO2 competes with NO for active sites available for adsorption

Steady state NO conversion at different NO2/NOx feed ratio

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Oxidation of NO (inhibition by H2O)

Effect of H2O studied at steady state conditions varying inlet H2O concentration Presence of H2O also found to inhibit NO oxidation reaction H2O may react with NO2 to form HNO2 and HNO3 which may block the active Fe sites

Steady state NO conversion at different H2O inlet concentrations

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Oxidation of NO (Kinetic model)

Kinetics of the reaction found under differential conditions
Component NO Order w.r.t. component ~1

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
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Kinetic model for NO oxidation

Rate expression:

fraction of vacant sites is given by

The mechanism takes into account the inhibition effects of H2O and NO2 Orders predicted by rate expression are similar to experimental observations

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Kinetics of SCR reaction system

Adsorption/desorption of NH3 on catalyst

Oxidation of NH3 to N2 and NOx (detrimental)

Oxidation of NO to NO2 (desirable)

SCR of NO with NH3

Assess mass transfer limitations Kinetic model development

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SCR (effect of NH3)

Standard SCR reaction considered:

4NH3 + 4NO + 4O2 4N2 + 6H2O

Experiments show the inhibition of reaction by NH3 Low temperature: Strong binding of NH3 to reaction sites is the likely cause of the inhibition High temperature: NH3 oxidation dominant

Rate of SCR for different inlet NH3 concentration at different temperatures

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SCR of NO with NH3

From differential experiments, power law model developed

a b g
E

1 0.55 0.3 42 kJ/mol

H2O does not hinder the reaction

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Kinetics of SCR reaction system

Adsorption/desorption of NH3 on catalyst

Oxidation of NH3 to N2 and NOx (detrimental)

Oxidation of NO to NO2 (desirable)

SCR of NO with NH3

Assess mass transfer limitations Kinetic model development

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Effect of mass transfer process

To measure true kinetics of SCR, mass transfer limitations should be negligible Washcoat diffusion Studies performed earlier by various groups show no or negligible mass transfer limitations at temperatures less than Transport to surface 300 oC . Understanding mass Flowing gases transfer limitations: Comparison of the characteristic times Weisz-Prater modulus ( >1 diffusion limitations)
Temperature range Weisz-Prater modulus () (oC) 150-300 SEM image of1 (No washcoat diffusion resistance) < washcoated Fe-zeolite catalyst 350-500 > 1 (significant washcoat diffusion resistance)
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Washcoat

Mass transfer limitations explored

Comparison between two samples was done at same gas flow rate
A
Catalyst loading Monolith length 11% 2 cm

B
22% 1 cm

(A) (B)

i.e.

kept constant
Comparison of NO conversion during SCR over sample A and B

Difference in conversion at high temperature shows presence of washcoat diffusion

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 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.
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Kinetics of SCR reaction system

Adsorption/desorption of NH3 on catalyst

Oxidation of NH3 to N2 and NOx (detrimental)

Oxidation of NO to NO2 (desirable)

SCR of NO with NH3

Assess mass transfer limitations Kinetic Model development

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Determination of RDS in SCR

Comparison of NO oxidation and SCR of NO
Order wrt NO NO Oxidation SCR of NO ~1 ~1 Order wrt O2 ~ 0.5 ~ 0.5 Eact (kJ/mol) 39 42

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

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Kinetic model development for SCR

Identification of reaction sites is necessary to develop kinetic model Effect of water:
Reaction NH3 adsorption NH3 oxidation NO oxidation

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)
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Kinetic model of SCR (reactions)

NO adsorption at S1 Oxygen adsorption at S1 Surface reaction NO2 desorption NH3 adsorption at S2 NH3 spillover (hindrance) Hindrance by water N2 formation, active sites getting free

N2 formation, active sites getting free

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Kinetic model for SCR

Langmuir-Hinshelwood mechanism:

Surface coverage of NO
Reaction between gas phase NO and adsorbed O Eley-Rideal mechanism:

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Transient experiments

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Transient experiments on SCR

NH pre-adsorbed on (NO Oxidation) Evolution of N2 started system started more realistic NO + O2 of NO started out to study Transient studies 3on supply2to the (SCR taking place) Evolution SCR carried the catalyst conditions encountered in vehicle

N2 evolution NH3 supply NO2 evolution stopped NO + O2 flow started

NH3 supply to catalyst

Transient experiment of standard SCR on commercial Fe-Zeolite catalyst (T = 150 oC)

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 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

N2 concentrations during transient experiments at different temperatures

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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
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Assessment of the paper

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Impact and merits of the paper

Detailed step by step analysis of reaction system is done Assumption of RDS is supported by experiments It is established that effects of mass transfer should be taken into account during modeling and analysis of the SCR reactor Proposed model for NO oxidation verified in subsequent publication 9 citations in last 10 months

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Shortcomings of the paper

Since heat of adsorption for NH3 is a function of coverage, fitting adsorption data to Temkin isotherm could have been possible Goodness of fitting Langmuir isotherm to the NH3 adsorption is not discussed While proposing the SCR kinetic mechanism, active sites have been considered as S1 and S2. However, Sites S1 and S2 are not identified in detail Identification of sites can help formulation of better catalyst

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Shortcomings of the paper

NO oxidation reaction: NO + O2 NO2 Mulla et al. showed that while considering NO oxidation kinetics, effect of inhibition by NO2 should be considered. Mulla et al. conclude, if the effect is not considered then the true activation energy is not calculated for the reaction Authors did not consider effect of NO2 inhibition while calculating the activation energy of NO oxidation Authors did not confirm which mechanism (LangmuirHinshelwood or Eley-Rideal) is more probable for SCR
Mulla et al., Catt. Lett. 2005. 40

Thank you

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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.
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2.
3. 4. 5. 6. 7.

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EPA NA Emission Standards

5.0 4.5

NOx g/hp-hr

4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0

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

Fig 2: NH3 TPD experiments at 500 ppm concentration

NH3 TPD experiments at different concentration

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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

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Fig 6: Product distribution of SCR reaction

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Fig 7: NO conversion in SCR (comparison of different catalyst)

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Fig 8: Effect of water on standard SCR

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 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

Fig 9: NO conversion with GSHV for SCR reaction

51

Fig 10: Effect of NO concentration on SCR reaction rate

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Fig 11: Effect of O2 concentration on SCR reaction rate

53

Fig 12: Effect of NH3 concentration on SCR reaction rate

54

Fig 13: Arrhenius plot for rate of NO conversion against inverse of catalyst temperature
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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

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