Federica Barontini

Gasification of pelletized biomass in a pilot scale downdraft gasifier

This work presents a pilot-scale investigation aimed at assessing the feasibility and reliability of biomass pellet gasification. Wood sawdust and sunflower seeds pellets were tested in a 200 kW downdraft gasifier operating with air as gasifying agent. The gasification of pelletized biomass led to rather high and unstable pressure drops, reducing the gasifier productivity and stability. Furthermore the generation of fine residues compromised the operation of wet ash removal systems. On the other hand, good syngas compositions (H(2) 17.2%, N(2) 46.0%, CH(4) 2.5%, CO 21.2%, CO(2) 12.6%, and C(2)H(4) 0.4%), specific gas production (2.2-2.4 N m(3) kg(-1)) and cold gas efficiency (67.7-70.0%) were achieved. For these reasons pelletized biomass should be considered only as complementary fuel in co-gasification with other feedstock.

Bio-oils from biomass slow pyrolysis: A chemical and toxicological screening

Bio-oils were produced from bench-scale slow-pyrolysis of three different biomass samples (corn stalks, poplar and switchgrass). Experimental protocols were developed and applied in order to screen their chemical composition. Several hazardous compounds were detected in the bio-oil samples analysed, including phenols, furans and polycyclic aromatic hydrocarbons. A procedure was outlined and applied to the assessment of toxicological and carcinogenic hazards of the bio-oils. The following hazardous properties were considered: acute toxicity; ecotoxicity; chronic toxicity; carcinogenicity. Parameters related to these properties were quantified for each component identified in the bio-oils and overall values were estimated for the bio-oils. The hazard screening carried out for the three bio-oils considered suggested that: (i) hazards to human health could be associated with chronic exposures to the bio-oils; (ii) acute toxic effects on humans and eco-toxic effects on aquatic ecosystems could also be possible in the case of loss of containment; and (iii) bio-oils may present a marginal potential carcinogenicity. The approach outlined allows the collection of screening information on the potential hazards posed by the bio-oils. This can be particularly useful when limited time and analytical resources reduce the possibility to obtain detailed specific experimental data.

Assessment of syngas composition variability in a pilot-scale downdraft biomass gasifier by an extended equilibrium model

A new simplified approach based on equilibrium modeling is proposed in this work to describe the correlations among syngas species experimentally observed in a pilot scale downdraft biomass gasifier operated with different feedstocks (biomass pellets and vine prunings). The modeling approach is based on experimental evidence on the presence of devolatilization products in the syngas and fluctuations of syngas composition during stationary operation, accounted for by introducing two empirical parameters, a by-pass index and a permeability index. The simplified model correctly reproduces the correlations among the main syngas species (including methane and ethylene) resulting from experimental data of pilot tests with different feedstocks and under a wide range of operating conditions.

Gasification of agricultural residues in a demonstrative plant: Corn cobs

Biomass gasification couples the high power efficiency with the possibility of valuably using the byproducts heat and biochar. The use of agricultural wastes instead of woody feedstock extends the seasonal availability of biomasses. The downdraft type is the most used reactor but has narrow ranges of feedstock specifications (above all on moisture and particle size distribution), so tests on a demonstrative scale are conducted to prove the versatility of the gasifier. Measurements on pressure drops, syngas flow rate and composition are studied to assess the feasibility of such operations with corn cobs. Material and energy balances, and performance indexes are compared for the four tests carried out under different biomass loads (66-85 kg/h). A good operability of the plant and interesting results are obtained (gas specific production of 2 m3/kg, gas heating value 5.6-5.8 MJ/m3, cold gas efficiency in the range 66-68%, potential net power efficiency 21.1-21.6%).

Coupling of chiral 1-bromo-1,2-dienes with zinc-based cuprates: a new procedure for the regio and stereoselective synthesis of functionalized acetylenic compounds

Abstract Zinc alkylcyanocuprates (Knochel reagents) are found to be active in the cross-coupling reaction with allenic bromides affording acetylenic products with a high regio and stereoselective 1,3- anti substitution. The coupling process, which has been successfully extended to functionalized cuprates, can also be performed with alkylzinc chlorides in the presence of catalytic amounts of cuprous salts.

Gasification of agricultural residues in a demonstrative plant: Vine pruning and rice husks.

Tests with vine pruning and rice husks were carried out in a demonstrative downdraft gasifier (350 kW), to prove the reactor operability, quantify the plant efficiency, and thus extend the range of potential energy feedstocks. Pressure drops, syngas flow rate and composition were monitored to study the material and energy balances, and performance indexes. Interesting results were obtained for vine pruning (syngas heating value 5.7 MJ/m(3), equivalent ratio 0.26, cold gas efficiency 65%, power efficiency 21%), while poorer values were obtained for rice husks (syngas heating value 2.5-3.8 MJ/m(3), equivalent ratio 0.4, cold gas efficiency 31-42%, power efficiency 10-13%). The work contains also a comparison with previous results (wood pellets, corn cobs, Miscanthus) for defining an operating diagram, based on material density and particle size and shape, and the critical zones (reactor obstruction, bridging, no bed buildup, combustion regime).

Development of a bi-equilibrium model for biomass gasification in a downdraft bed reactor.

This work proposes a simple and accurate tool for predicting the main parameters of biomass gasification (syngas composition, heating value, flow rate), suitable for process study and system analysis. A multizonal model based on non-stoichiometric equilibrium models and a repartition factor, simulating the bypass of pyrolysis products through the oxidant zone, was developed. The results of tests with different feedstocks (corn cobs, wood pellets, rice husks and vine pruning) in a demonstrative downdraft gasifier (350kW) were used for validation. The average discrepancy between model and experimental results was up to 8 times less than the one with the simple equilibrium model. The repartition factor was successfully related to the operating conditions and characteristics of the biomass to simulate different conditions of the gasifier (variation in potentiality, densification and mixing of feedstock) and analyze the model sensitivity.

An insight into the molecular mechanism of the masking process in titanium tanning

Among the alternative mineral tanning agents investigated for replacing chromium, titanium (IV)-based salts are one of the most promising ones for the development of novel and cleaner tanning processes in the leather industry. The molecular mechanism of the solvation of titanyl salts and their interaction with masking agents was investigated in the present work. A computational study based on the quantum mechanical density functional theory was carried out, focusing on the behavior of complexes between titanyl oligomers of suitable length and different masking agents. The optimized structure of a titanyl octamer was calculated. Different carboxylic acids, and their corresponding anions, containing at least two polar functional groups suitable for the complexation of the titanyl, were considered as masking agents: glycolic, lactic, malic, citric, and phthalic acid. The most significant geometric and energetic parameters of the different titanyl-masking agent complexes were calculated. The results obtained indicate that the lactic acid system shows the best binding energies and the best flexibility. The OH–CRR’–COOH structure appears to be well fitted to complex the titanyl chain. The effect of the R and R’ sidechains on complex stabilization seems to be related to electrostatic factors (presence of charge) rather than to steric hindrance.