Novel Hot Vapor Filter Design for Biomass Pyrolysis.

Fast pyrolysis is a mature technology for the conversion of solid biomass into a liquid intermediate, fast pyrolysis bio-oil (FPBO). FPBO has so far been used mainly as heating fuel, but the target is to use it for the production of sustainable fuels and chemicals in the future. In the pyrolysis process, inorganic materials (ash) from the biomass are mostly sequestered in char particles, which can be separated with cyclones. Small particles (<10 µm) escape the cyclones and condense with vapors. In bio-oils, these solid materials are unfavorable because they can cause erosion, corrosion, and blockages at injection nozzles in power generation systems and deactivate the catalyst in bio-oil upgrading. Hot vapor filtration using either moving bed or barrier filters has been tested on a small scale for the removal of fine particles from the pyrolysis vapors. The challenges with these filter types have been the increased pressure drop across the filter with time, inefficient solid removal, and loss in organics. A new hot vapor filter combining both a barrier filter and a moving bed filter was constructed and tested to overcome these problems. In this filter system, the filter elements are inserted in a vessel, where hot sand flows through to continuously remove the cake over filter candles. The filter was successfully tested with stem chips, contaminated wood, and forest residue for 6-8 h without any pressure increase. The organic liquid yield decreased in the best case only by 3 wt % using the lowest filtration temperature and shortest residence time. The oil properties were slightly affected by cracking of the sugar fraction, which decreased the oxygen content, microcarbon residue, and carbonyl content but increased the acidity. Only minor improvements in metal removal were seen due to the high detection limits of metal analysis.

Improving Fast Pyrolysis Bio-Oil Yield and Quality by Alkali Removal from Feedstock.

Alkali removal from forest residues, eucalyptus residues, and wheat straw was studied by water and dilute nitric acid leaching. Leaching parameters were optimized for each feedstock in laboratory-scale experiments. After the optimization of leaching on the laboratory scale, nitric acid-leached and untreated feedstocks were pyrolyzed in a bench-scale bubbling fluidized bed unit. In the case of eucalyptus residues and wheat straw, nitric acid leaching was found to increase the organic liquid yield compared to untreated feedstock. In addition, the sugar content of the fast pyrolysis bio-oils was increased, and the alkali content reduced. On the other hand, the pyrolysis experiments with acid-leached forest residues were unsuccessful due to the bed agglomeration. These problems are expected to be a result of the lack of catalytically active elements in biomass which enhance especially the cracking reactions of lignin. Finally, the results were demonstrated in the pilot-scale unit where nitric acid-leached oat straw was pyrolyzed with high organic liquid yield.

Analysis of Lipophilic Extractives from Fast Pyrolysis Bio-Oils.

Fast pyrolysis bio-oils (FPBOs) originating from forest residues contain extractive-derived substances, which may form a separate, sticky layer with char particles on the surface of these bio-oils. In this study, first, the removal of extractive-derived substances from the bio-oil top phase was studied by common solvents with different polarities. In this case, the results indicated that when aimed at the maximum yield of single-phase fuel oil and thus the maximum amount of extractives removed, the use of n-heptane or n-hexane seems to be of benefit for this purpose. For safety reasons, the use of n-heptane was recommended. Second, an analysis practice (extraction time and the way of mixing) was optimized. In order to reduce the extraction time and enhance the extraction yield, it was important to break the oil surface in extraction. Third, based on the characterization results of the n-heptane extract by gas chromatography and ultraviolet spectroscopy, the detected compounds were classified as fatty acids, resin acids, esterified fatty acids, terpenoids, and steroids, and their total content (27 wt %) was lower than that of lignin-derived compounds (70 wt %). The extraction of the FPBO top phase with n-heptane followed by this analysis practice was a useful way to estimate the content and composition of lipophilic extractives.

Valorization of Eucalyptus, Giant Reed Arundo, Fiber Sorghum, and Sugarcane Bagasse via Fast Pyrolysis and Subsequent Bio-Oil Gasification.

Fast pyrolysis of giant reed Arundo (Arundo donax), fiber sorghum (Sorghum bicolor L.Moench), eucalyptus (Eucalyptus spp.), and sugarcane bagasse (Saccharum officinarum) was studied in bench-scale bubbling fluidized bed reactor. Product yields were determined, and detailed physicochemical characterization for produced fast pyrolysis bio-oils (FPBOs) was carried out. The highest organic liquid yield (dry basis) was observed with sugarcane bagasse (59-62 wt %), followed by eucalyptus (49-53 wt %), giant reed Arundo (39 wt %), and fiber sorghum (34-42 wt %). After the pyrolysis experiments, produced FPBOs were gasified in an oxygen-blown autothermal catalytic reforming system for the produced synthesis gas. The gasifier consists of a partial oxidation zone where the FPBO is gasified, and the raw syngas is then reformed over a fixed bed steam-reforming catalyst in the reforming zone. The gas production (∼1.7 Nm3/kg FPBO) and composition (H2 ∼ 50 vol %, CO 20-25 vol %, and CO2 25-30 vol %) were similar for all FPBOs tested. These results show that the combination of fast pyrolysis with subsequent gasification provides a technically feasible and feedstock flexible solution for the production of synthesis gas.

Evaluation of Analysis Methods for Formaldehyde, Acetaldehyde, and Furfural from Fast Pyrolysis Bio-oil.

Fast pyrolysis bio-oil (FPBO), a second-generation liquid bioenergy carrier, is currently entering the market. FPBO is produced from biomass through the fast pyrolysis process and contains a large number of constituents, of which a significant part is still unknown. Various analytical methods have been systematically developed and validated for FPBO in the past; however, reliable methods for characterization of acetaldehyde, formaldehyde, and furfural are still lacking. In this work, different analysis methods with (HS-GC/ECD, HPLC, UV/Vis) and without derivatization (GC/MSD, HPLC) for the characterization of these components were evaluated. Five FPBO samples were used, covering a range of biomass materials (pine wood, miscanthus, and bark), storage conditions (freezer and room temperature), and after treatments (none, filtration, and vacuum evaporation). There was no difference among the methods for the acetaldehyde analysis. A significant difference among the methods for the determination of formaldehyde and furfural was observed. Thus, more data on the accuracy of the methods are required. The precision of all methods was below 10% with the exception of the HPLC analysis of acetaldehyde with an RSD of 14%. The concentration of acetaldehyde in the FPBO produced from the three different biomasses and stored in a freezer after production ranged from 0.24 to 0.60 wt %. Storage at room temperature and vacuum evaporation both decreased significantly the acetaldehyde concentration. Furfural concentrations ranged from 0.11 to 0.36 wt % for the five samples. Storage and after treatment affected the furfural concentration but to a lesser extent than for acetaldehyde. Storage at room temperature decreased formaldehyde similarly to acetaldehyde; however, after vacuum-evaporation the concentration of formaldehyde did not change. Thus, the analysis results indicated that in FPBO the equilibrium of formaldehyde and methylene glycol is almost completely on the methylene glycol side, as in aqueous solutions. All three methods employed here actually measure the sum of free formaldehyde and methylene glycol (FAMG).

Bio-oil production of softwood and hardwood forest industry residues through fast and intermediate pyrolysis and its chromatographic characterization.

Bio-oils were produced through intermediate (IP) and fast pyrolysis (FP), using Eucalyptus sp. (hardwood) and Picea abies (softwood), wood wastes produced in large scale in Pulp and Paper industries. Characterization of these bio-oils was made using GC/qMS and GC×GC/TOFMS. The use of GC×GC provided a broader characterization of bio-oils and it allowed tracing potential markers of hardwood bio-oil, such as dimethoxy-phenols, which might co-elute in 1D-GC. Catalytic FP increased the percentage of aromatic hydrocarbons in P. abies bio-oil, indicating its potential for fuel production. However, the presence of polyaromatic hydrocarbons (PAH) draws attention to the need of a proper management of pyrolysis process in order to avoid the production of toxic compounds and also to the importance of GC×GC/TOFMS use to avoid co-elutions and consequent inaccuracies related to identification and quantification associated with GC/qMS. Ketones and phenols were the major bio-oil compounds and they might be applied to polymer production.

SANS analysis of the microstructural evolution during the aging of pyrolysis oils from biomass.

In this paper, we report for the first time a microstructural characterization of pyrolysis oils obtained from biomass. Bio crude oils (BCOs) are good candidates as substitutes for mineral oils as fuels. By using small-angle neutron scattering (SANS), we show that BCOs are nanostructured fluids constituted by a complex continuous phase and nanoparticles mainly formed by the association of units of pyrolytic lignins. The aggregation of these units during the time produces branched structures with fractal dimension D(f) between 1.4 and 1.5, which are responsible for BCO aging. SANS results fully support the recently formulated thermal ejection theory, accounting for the mechanism of formation of the lignin fraction in oils obtained from fast pyrolysis of biomass.