Catalytic Supercritical Water Gasification of Sewage Sludge/Secondary Pulp/Paper-Mill Sludge for Hydrogen Production

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Zhang, Linghong
Biomass , Bio-Energy , Supercritical Water Gasification , Liquefaction , Hydrogen , Catalyst
Supercritical water gasification (SCWG) is an innovative hydrothermal technique, employing supercritical water (SCW, T≥374oC, P≥22.1 MPa) as the reaction media, to convert wet biomass or aqueous organic waste directly into hydrogen (H2)-rich synthetic gas (syngas). In the first stage of this research, a secondary pulp/paper-mill sludge (SPP, provide by AbitibiBowater Thunder Bay Operations) was gasified at temperatures of 400-550oC for 20 to 120 min in a high-pressure batch reactor for H2 production. The highest H2 yield achieved was 14.5 mol H2/kg SPP (on a dry basis) at 550oC for 60 min. In addition, SPP exhibited higher H2-generation potential than sewage sludges, likely attributed to its higher pH and higher volatile matter and alkali salt contents. In the second stage, a novel two-step process for sludge treatment was established. The first step involved the co-liquefaction of SPP with waste newspaper in a batch reactor at varying mixing ratios, aimed at converting the organic carbons in the feedstocks into valuable bio-crude and water-soluble products. The highest heavy oil (HO) yield (26.9 wt%) was obtained at 300oC for 20 min with a SPP-to-newspaper ratio of 1:2. This co-liquefaction process transformed 39.1% of the carbon into HOs, where 16.3% of the carbon still remained in the aqueous waste. Next, an innovative Ru0.1Ni10/γ-Al2O3 catalyst (10 wt% Ni, Ru-to-Ni molar ratio=0.1), with long-term stability and high selectivity for H2 production, was developed for the SCWG of 50 g/L glucose, where no deactivation was observed after 33 h on stream at 700oC, 24 MPa and a WHSV (weight hourly space velocity) of 6 h-1. The H2 yield was maintained at ~50 mol/kg feedstock. The addition of small amounts of Ru to Ni10/γ-Al2O3 was found to be effective in enhancing Ni dispersion and increasing the reducibility of NiO. Finally, the Ru0.1Ni10/γ-Al2O3 catalyst together with an activated carbon (AC) supported catalyst (Ru0.1Ni10/AC) were utilized for treating the aqueous by-product from sludge-newspaper co-liquefaction using a continuous down-flow tubular reactor. More than 90% of the carbon in the waste was destroyed at 700oC with the highest H2 yield of 71.2 mol/kg carbon noted using Ru0.1Ni10/AC.
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