Novel diatomite (R1) and maifanite (R2) were utilized as support materials in an up-flow anaerobic sludge bed (UASB) reactor for the treatment of recalcitrant petroleum wastewater. At high organic loadings (11 kg-COD/m(3) . d), these materials were efficient at reducing COD (92.7% and 93.0%) in comparison with controls (R0) (88.4%). Higher percentages of large granular sludge (0.6 mm or larger) were observed for R1 (30.3%) and R2 (24.6%) compared with controls (22.6%). The larger portion of granular sludge provided a favorable habitat that resulted in greater microorganism diversity. Increased filamentous bacterial communities are believed to have promoted granular sludge formation promoting a conductive environment for stimulation methanogenic Archaea. These communities had enhanced pH tolerance and produced more methane. This study illustrates a new potential use of diatomite and maifanite as support materials in UASB reactors for increased efficiency when treating refractory wastewaters. (C) 2017 Elsevier Ltd. All rights reserved.