Selective Catalytic Reduction of NOX by NH3 for Diesel Exhaust Aftertreatment

Open Access
Author:
Sokolowski, Christopher Henry
Graduate Program:
Energy and Mineral Engineering
Degree:
Master of Science
Document Type:
Master Thesis
Date of Defense:
April 21, 2014
Committee Members:
  • Yongsheng Chen, Thesis Advisor
  • Sarma V Pisupati, Thesis Advisor
  • Jonathan P Mathews, Thesis Advisor
Keywords:
  • selective catalytic reduction
  • SCR
  • NH3-SCR
  • diesel
  • NOX
  • nitrogen oxides
  • catalyst deactivation
  • zeolite
  • iron zeolite
Abstract:
The increasing price of liquid fuels and an increased focus on fuel efficiency has driven vehicle engine manufacturers toward diesel and other lean burn engines at the cost of increased emissions of nitrogen oxides (NOX), which contribute to pollution such as smog, ground level ozone, and acid deposition. Within the past thirty years, increasingly stringent NOX emission standards have forced engine manufacturers to develop novel ways to reduce these emissions. With the implementation of the latest American and European NOX emission standards, Selective Catalytic Reduction (SCR) has become the most prominent NOX reduction method in lean-burn engines. In the present work, a method is developed to test the performance of commercial SCR catalyst coated monoliths and probe the deactivation mechanisms. A monolith testing apparatus is constructed for these purposes. Necessary design features included a programmable gas mixing system, a steam generator, a temperature control system, and an analysis system based upon Fourier-transformed infrared spectroscopy. It is found that a high flow rate of carrier gas as well as a method to generate a water mist and prevent dripping is essential to ensure a stable supply of steam and repeatable results. Important SCR reactions, namely the standard, fast, and slow SCR reactions as well as NH3 adsorption and performance of a zeolite catalyst coated monolith were investigated at three temperatures – 250 and 300 °C representing engine operation at normal operating conditions and 400 °C representing engine operation at high load. The amount of NH3 adsorbed decreased with temperature in line with previous studies while NOX reduction performance increased with higher temperatures at all inlet compositions tested. A transient drop in NO conversion performance was observed upon introduction of NH3 without the presence of NO2 consistent with previous studies suggesting an NH3 inhibition mechanism. When supplied with 1:1 and 1:3 ratios of NO:NO2 at 250 °C, the catalyst reduced more NOX than NH3 suggesting that part of the NOX reduction was proceeding through an ammonium nitrate intermediate and generating nitric acid. In addition, NH3 oxidation into N2O was prevalent at 300°C in an excess of NO2. The SCR reaction results indicate that both transient effects and side reactions play an important role in an NH3 SCR system, particularly one that is designed to operate under continuously changing conditions. Catalyst aging mechanisms were investigated by comparing catalytic performance, material structure, and surface composition of a new and a used zeolite catalyst monolith for the fast SCR reaction. Physical analysis of the catalyst monoliths through X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD), and Scanning Electron Microscopy (SEM) with Energy-Dispersive X-ray Spectroscopy (EDS) indicated four aging mechanisms. Both the new and used catalyst monoliths performed at least 95% NOX reduction in the fast reaction at all temperatures tested. Despite the similar NOX reduction performance, the used catalyst monolith exhibited lower NO oxidation performance, increased NH3 oxidation, and a lower quantity of adsorbed NH3 compared to the new catalyst monolith. Dealumination is likely the primary cause of the used catalyst monolith’s lower NOX reduction performance with promoter metal deactivation, poisoning by sulfur and phosphorous, and mechanical failure of the catalyst coating on the monolith also contributing to the decreased performance. The results do not find evidence of carbon coking. This investigation into catalyst aging mechanisms confirms the efficacy of the commercial SCR catalyst monolith over long time periods.