Removal of silica in rice husk derived Ni/biochar modifies reaction intermediates formed and minimizes coking in steam reforming of glycerol

Abstract

Metal/biochar catalyst features with the advantages for easy recovery of chemical energy of biochar carrier and metal species via simply combustion. Another unique feature of biochar carrier is intrinsic inorganic species, which might also interact with metal species in resulting catalyst. This was investigated herein by synthesis of the Ni/biochar with rice husk-derived biochar carrier pretreated with NaOH for removal of SiO2 and evaluation of the resulting catalysts in steam reforming of glycerol. The solid phase reactions between NaOH and biochar (mass ratio: 2) plus subsequent washing removed 94.6% of ash (mainly SiO2). This formed Ni/biochar of fragmented surface with specific surface area increasing from 207.8 to 457.4 m2g-1 and simultaneously increasing mesopore percentage from 15.5% to 24.0%. NaOH treatment also effectively removed significant portion of both Lewis and Brønsted acidic sites but created abundant alkaline sites. These drastically enhanced nickel dispersion and activity for steam reforming. In-situ IR characterization suggested enhanced adsorption/activation of CO2 and H2O over Ni/biochar treated with NaOH (Ni/biochar-NaOH), which mitigated accumulation of coke precursors bearing CO or CC via accelerated gasification reactions. This led to the reduced amount of coke (mass ratio to catalyst) from 193.4% to 94.7% over Ni/biochar treated with 2-fold of NaOH or to 111.3% over Ni/biochar treated with 1-fold of NaOH. The coke formed was mainly catalytic type in form of carbon nanotube over Ni/biochar-NaOH. The superior resistivity to coking originated from developed pores, enhanced Ni dispersion and abundant alkaline sites from the NaOH treatment.