Materials Challenges in Reverse-Flow Pyrolysis Reactors for Petrochemical Applications

Currently, the pyrolysis of hydrocarbons for the production of light olefins is almost exclusively carried out in steam crackers operating around 900-1000 degrees C. However, cracking hydrocarbons at much higher temperature results in high selectivity to acetylene, which can be converted into many petrochemical products including ethylene. The desired hydropyrolysis reaction from hydrocarbons to acetylene can be realized in a reverse-flow reactor at very high temperatures (>1700 degrees C) in a scalable manner. The reactor elements include ceramic components that are placed in the hottest regions of the reactor and must withstand a temperature that is in the range of 1500-2000 degrees C. In addition, the temperature rises and falls with the reverse-flow cycle; a fluctuation that could be as high as 100-500 degrees C over a period of several seconds. Moreover, the materials in the hot zone are exposed alternately to a regeneration (heat addition) step that is mildly oxidizing, and a pyrolysis (cracking) step that is strongly reducing with a correspondingly high carbon activity. This article addresses the thermodynamic stability of selected ceramic materials based on alumina, zirconia, and yttria for such an application. Results from laboratory tests involving the exposure of these ceramic materials to simulated process conditions followed by their microstructural characterization are compared with expectations from thermodynamic predictions.