Effect of Phosphine on Coke Formation during Steam Cracking of Propane

In conventional steam cracking feedstocks, contaminants such as sulfur, phosphine, and heavy metal components, present in trace levels, are believed to affect coke formation on high temperature alloys. To gain an understanding of the role of phosphine coking rates on 25/35, CrNi and Al-containing reactor materials were determined in a plug flow reactor during cracking of a propane feedstock doped with ppb levels of PH₃ in the presence of DMDS. The presence of phosphine decreased the asymptotic coking rates by more than 20%, while it had a smaller influence on the catalytic coking rate. The coking rate was more severely reduced for the 25/35 CrNi alloy in comparison to the Al-containing alloy. The ppm levels of phosphine did not affect the olefin yields nor the production of undesired carbon monoxide. The morphology of the coked alloys were studied using an off-line Scanning Electron Microscope with Energy Dispersive X-ray detector (SEM with EDX) images of coked coupons. Two types of coke morphology are observed, i.e., filamentous coke with DMDS as an additive and globular coke in the presence of phosphine. The effect of phosphine on the material has a positive impact on the oxide scale homogeneity of 25/35 CrNi alloy, whereas the Al-containing alloy remained unchanged.