Dry-bed
adsorptive desulfurization of biomass-based syngas with
low to medium sulfur content using ZnO was investigated as an alternative
to the conventional wet scrubbing processes. The technical feasibility
of ZnO-based desulfurization was studied in laboratory-scale H2S breakthrough experiments. The experiments were set up to
utilize realistic H2S concentrations from gasification
and therefore long breakthrough times. Experiments were performed
in a steam-rich model biosyngas in varying conditions. The long-term
breakthrough experiments showed apparent ZnO utilization rates between
10 and 50% in the tested conditions, indicating intraparticle mass-transfer
resistances partly due to space velocity and particle size constraints
as well as the most likely product-layer resistances as evidenced
by the large spent adsorbent surface area decrease. An empirical deactivation
model to estimate full breakthrough curves was fitted to the laboratory-scale
experimental data. Breakthrough experiment in tar-rich syngas was
also performed with the conclusion that ZnO performance is not significantly
affected by hydrocarbons despite carbon deposition on the particle
surfaces.
A flexible combined heat, power and fuel production concept, FlexCHX, is being developed for managing the seasonal mismatch between solar energy supply and the demand for heat and power characteristic of Northern and Central Europe. The process produces an intermediate energy carrier (Fischer-Tropsch hydrocarbon product), which can be refined to transportation fuels using existing refineries. The FlexCHX process can be integrated into various combined heat and power production systems, both industrial CHPs and communal district heating units. In the summer season, renewable fuels are produced from biomass and hydrogen; the hydrogen is produced from water via electrolysis that is driven by low-cost excess electricity from the grid. In the dark winter season, the plant is operated only with biomass in order to maximize the production of the much-needed heat, electricity and FT hydrocarbons. Most of the invested plant components are in full use throughout the year with only the electrolysis unit being operated seasonally. The catalytic reformer plays a key role in this process by converting tars and light hydrocarbon gases into synthesis gas and by bringing the main gas constituents towards equilibrium. Developmental precious metal catalysts were used, and an optimal reformer concept was established and tested at pilot scale. Reforming results obtained at pilot gasification tests with commercial nickel catalysts and with the developed precious metal catalysts are presented.
Dry-bed adsorptive desulfurization of biomass-based syngas with
a low- to medium sulfur content
using ZnO was studied as an alternative to conventional wet-scrubbing
processes for a small- to medium-scale biomass-to-liquid process concept.
Following laboratory-scale long-term H2S breakthrough experiments
in a previous study, desulfurization tests were scaled-up to bench-scale
with actual bio-syngas to verify the lab-scale results under more
realistic process conditions. A desulfurization unit was constructed
and connected to a steam-blown atmospheric pilot-scale fluidized bed
gasifier. Two successful 70+ h test campaigns were conducted with
H2S removal below the breakthrough limit using full-sized
ZnO adsorbent particles. Scanning electron microscopy (SEM), energy-dispersive
X-ray spectroscopy elemental analysis, and Brunauer–Emmett–Teller
(BET) surface area characterization of the fresh and spent adsorbent
pellets were performed. SEM micrographs displayed the outward enlarging
particle size in the sulfided layer. Characterization showed significant
core–shell sulfidation behavior with a few hundred micron-thick
sulfided layer leaving the majority of ZnO unutilized. Adsorbents
lost most of their porosity in use, which was evident from BET surface
area results. Simultaneous COS removal was found possible by the hydrolysis
reaction to H2S. Furthermore, evidence of minor chlorine
adsorption was found, thus highlighting the need for a dedicated HCl
removal step upstream of desulfurization.
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