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Selective Catalytic Reduction of NOx over V2O5-WO3-TiO2 SCR Catalysts—A Study at Elevated Pressure for Maritime Pre-turbine SCR Configuration

  • Steen R. Christensen
  • Brian B. Hansen
  • Kim H. Pedersen
  • Joakim R. Thøgersen
  • Anker D. JensenEmail author
Article
  • 28 Downloads

Abstract

The selective catalytic reduction (SCR) of NOx using NH3 was studied at pressures up to 5 bar over a vanadium-based SCR catalyst (~1 wt% V2O5 and 10 wt% WO3/TiO2), relevant for the installation of SCR reactors upstream of the turbocharger at marine engines. Experiments were performed using both granulated catalyst in a lab-scale fixed-bed reactor and a monolith catalyst in a bench-scale setup. The residence time across the catalytic bed was kept constant, by increasing the (normalized (0 °C, 1 atm)) volumetric flow rate proportionally to the pressure. The results show that for the granulated catalyst, the NOx conversion was independent of the pressure, indicating that the SCR kinetics are not affected by the increased pressure up to 5 bar. NH3 temperature-programmed desorption experiments showed that the catalyst NH3 adsorption increased with more than 30% when the pressure was increased from 1 bar to 4.5 bar. On the other hand, when the adsorption temperature was increased from 150 to 300 °C, the adsorption capacity decreased by approximately 60% independent on the pressure. The SCR reaction was unaffected by the increased NH3 uptake caused by the increased pressure, because only a certain fraction of the sites (\( {\theta}_{N{H}_3}^{\ast } \) = 0.14) was found to be active in the SCR reaction, and these are filled up at lower NH3 partial pressure than the total number of sites. Experiments using a monolithic catalyst showed that at temperatures above 250 °C, the NOx conversion was lower at an increased pressure (3.1 bar) when the residence time was held constant. This decrease was ascribed to increased internal and external diffusion limitations at the elevated pressure.

Keywords

Pre-turbo SCR SCR of NOx on ships High-pressure SCR of NOx NH3 TPD V/W/Ti catalyst 

Abbreviations

ABS

Ammonium bisulfate

ANR

Ammonia to NOx ratio

AS

Ammonium sulfate

CPSI

Channels per square inch

CSTR

Continuous stirred tank reactor

EGR

Exhaust gas recirculation

IMO

International maritime organization

LNG

Liquid natural gas

NECA

NOx emission control area

NOx

Nitrogen oxides, the sum of NO and NO2

PBR

Packed bed reactor

RSS

Residual sum of squares

SCR

Selective catalytic reduction

SECA

SOx emission control area

SOx

Sulfur oxides, the sum of SO2, SO3, and H2SO4

V-SCR

Vanadium-based SCR catalyst

Symbols

α

Temkin kinetics parameter [−]

CNH3

NH3 concentration [mol/m3]

dparticle

Catalyst particle diameter [m]

Dreactor

Reactor tube diameter [m]

DAB

Binary diffusion coefficient [m/s2]

dh

Hydraulic diameter [m]

ε

Porosity [−]

Ea

Activation energy of the adsorption process of NH3 [J/mol]

\( {E}_d^0 \)

Activation energy for the desorption process of NH3 [J/mol]

f

Friction factor [−]

Gz

Graetz dimensional number [−]

kNO

NO first order rate constant [1/s]

kNO

Mass based NO first order rate constant [m3/s/kg]

\( {k}_a^0 \)

Pre-exponential factor of the adsorption process of NH3 [m3/mol/s]

\( {k}_d^0 \)

Pre-exponential factor for the desorption process of NH3 [1/s]

\( {K}_{{\mathrm{NH}}_3} \)

NH3 adsorption equilibrium constant [m3/mol]

k(Tref)

Reaction rate constant calculate at the temperature Tref

L

Length of catalyst [m]

Ω

NH3 adsorption capacity (mol/m3 particles)

\( \varOmega ={\varOmega}^{\prime}\cdot \frac{1-\varepsilon }{\varepsilon } \)

NH3 adsorption capacity (mol/m3 reactor)

Preactor

Reactor pressure [Pa]

Q0

Volumetric flow rate (normal (0 °C, 1 atm)) [Nm3/s]

ra

Rate of adsorption of NH3 [1/s]

rd

Rate of desorption of NH3 [1/s]

Re

Reynolds dimensional number [−]

ρ

Density of catalyst [kg/m3]

rNO

Rate of NO disappearance [1/s]

Sc

Schmidts dimensional number [−]

Sh

Sherwood dimensional number [−]

Sh

Asymptotic Sherwood number [−]

θ

Surface coverage of NH3 [−]

\( {\theta}_{{\mathrm{NH}}_3}^{\ast } \)

Fraction of active sites in the SCR reaction [−]

θv

Surface coverage of vanadium [−]

U

Linear velocity [m/s]

V

Volume [m3]

v0

volumetric flow rate [m3/s]

W

Weight of catalyst [kg]

ymeas

Vectors containing the measured gas phase mole fraction [ppm]

ymodel

Vectors containing the modeled gas phase mole fraction [ppm]

z

Axial coordinate [m]

Z*

Dimensionless axial coordinate [−]

Notes

Acknowledgments

This work is part of the Danish societal partnership, Blue INNOship, and partly funded by the Innovation Fund Denmark (IFD) under File No: 155-2014-10 and the Danish Maritime Fund. The authors gratefully acknowledge the funding support.

Compliance with Ethical Standards

The authors declare that they have no competing interests.

Supplementary material

40825_2019_127_MOESM1_ESM.docx (4.7 mb)
ESM 1 (DOCX 4763 kb)

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Authors and Affiliations

  1. 1.Department of Chemical and Biochemical EngineeringTechnical University of DenmarkKgs. LyngbyDenmark
  2. 2.Umicore Denmark ApSKgs. LyngbyDenmark

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