Infrared Spectroscopy for Online Measurement of Tars, Water, and Permanent Gases in Biomass Gasification.

Online measurements of the raw gas composition, including tars and water, during biomass gasification provide valuable information in fundamental investigations and for process control. Mainly consisting of hydrocarbons, tars can, in principle, be measured using Fourier transform infrared (FT-IR) spectroscopy. However, an instrument subjected to raw gas runs the risk of condensation of tars on optical components and subsequent malfunction. Therefore, an external cell, heated to at least 400 ℃, has been designed to ensure that tars remain in the gas phase during FT-IR measurements. The cell was used for on-line FT-IR measurements of permanent gases (CO, CO2, CH4), water, and tars during the operation of a lab-scale downdraft gasifier using wood pellets, bark pellets, and char chips. Based on calibration, the measurement error of permanent gases was estimated to be 0.2%. Concentrations evaluated from spectral signatures of hydrocarbons in tar are in good agreement with results from solid-phase adsorption measurements and correlated well with operational changes in the gasifier.

Release of carbon nanotubes during combustion of polymer nanocomposites in a pilot-scale facility for waste incineration.

Nanocomposites, formed by incorporating nanoparticles into a matrix of standard materials, are increasing on the market. Little focus has been directed towards safe disposal and recycling of these new materials even though the disposal has been identified as a phase of the products' life cycle with a high risk of uncontrolled emissions of nanomaterials. In this study, we investigate if the carbon nanotubes (CNTs), when used as a filler in two types of polymers, are fully destructed in a pilot-scale combustion unit designed to mimic the combustion under waste incineration. The two polymer nanocomposites studied, polycarbonate (PC) with CNT and high-density polyethylene (HDPE) with CNT, were incinerated at two temperatures where the lower temperature just about fulfilled the European waste incineration directive while the upper was chosen to be on the safe side of fulfilling the directive. Particles in the flue gas were sampled and analysed with online and offline instrumentation along with samples of the bottom ash. CNTs could be identified in the flue gas in all experiments, although present to a greater extent when the CNTs were introduced in PC as compared to in HDPE. In the case of using PC as polymer matrix, CNTs were identified in 3-10% of the analysed SEM images while for HDPE in only ~0.5% of the images. In the case of PC, the presence of CNTs decreased with increasing bed temperature (from 10% to 3% of the images). The CNTs identified were always in bundles, often coated with remnants of the polymer, forming particles of ~1-4 µm in diameter. No CNTs were identified in the bottom ash, likely explained by the difference in time when the bottom ash and fly ash are exposed to high temperatures (~hours compared to seconds) in the pilot facility. The results suggest that the residence time of the fly ash in the combustion zone is not long enough to allow full oxidation of the CNTs. Thus, the current regulation on waste incineration (requiring a residence time of the flue gas >850 °C during at least 2 s) may not be enough to obtain complete destruction of CNTs in polymer composites. Since several types of CNTs are known to be toxic, we stress the need for further investigation of the fate and toxicity of CNTs in waste treatment processes.

Molecular characterization and optical properties of primary emissions from a residential wood burning boiler.

Modern small-scale biomass burners have been recognized as an important renewable energy source because of the economic and environmental advantages of biomass over fossil fuels. However, the characteristics of their gas and particulate emissions remain incompletely understood, and there is substantial uncertainty concerning their health and climate impacts. Here, we present online measurements conducted during the operation of a residential wood-burning boiler. The measured parameters include gas and particle concentrations, optical absorption and chemical characteristics of gases and particles. Positive matrix factorization was performed to analyze data from a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) equipped with a filter inlet for gases and aerosols (FIGAERO). Six factors were identified and interpreted. Three factors were related to the chemical composition of the fuel representing lignin pyrolysis products, cellulose/hemicellulose pyrolysis products, and nitrogen-containing organics, while three factor were related to the physical characteristics of the emitted compounds: volatile compounds, semi-volatile compounds, and filter-derived compounds. An ordinal analysis was performed based on the factor fractions to identify the most influential masses in each factor, and by deconvoluting high-resolution mass spectra fingerprint molecules for each factor were identified. Results from the factor analysis were linked to the optical properties of the emissions, and lignin and cellulose/hemicellulose pyrolysis products appeared to be the most important sources of brown carbon under the tested burning conditions. It is concluded that the emissions from the complex combustion process can be described by a limited set of physically meaningful factors, which will help to rationalize subsequent transformation and tracing of emissions in the atmosphere and associated impacts on health and climate.

Sulfur recirculation for increased electricity production in Waste-to-Energy plants.

Sulfur recirculation is a new technology for reducing boiler corrosion and dioxin formation. It was demonstrated in full-scale tests at a Waste to Energy plant in Göteborg (Sweden) during nearly two months of operation. Sulfur was recirculated as sulfuric acid from the flue gas cleaning back to the boiler, thus creating a sulfur loop. The new technology was evaluated by extensive measurement campaigns during operation under normal conditions (reference case) and operation with sulfur recirculation. The chlorine content of both fly ash and boiler ash decreased and the sulfur content increased during the sulfur recirculation tests. The deposit growth and the particle concentration decreased with sulfur recirculation and the dioxin concentration (I-TEQ) of the flue gas was reduced by approximately 25%. Sulfuric acid dew point measurements showed that the sulfuric acid dosage did not lead to elevated SO3 concentrations, which may otherwise induce low temperature corrosion. In the sulfur recirculation corrosion probe exposures, the corrosion rate decreased for all tested materials (16Mo3, Sanicro 28 and Inconel 625) and material temperatures (450 °C and 525 °C) compared to the reference exposure. The corrosion rates were reduced by 60-90%. Sulfur recirculation prevented the formation of transition metal chlorides at the metal/oxide interface, formation of chromate and reduced the presence of zinc in the corrosion products. Furthermore, measured corrosion rates at 525 °C with sulfur recirculation in operation were similar or lower compared to those measured at 450 °C material temperature in reference conditions, which corresponds to normal operation at normal steam temperatures. This implies that sulfur recirculation allows for higher steam data and electricity production without increasing corrosion.

Optical and mass spectrometric study of the pyrolysis gas of wood particles.

A detailed experimental investigation has been made of the pyrolysis--the first step in biomass combustion--of single birchwood particles. In addition to mass spectrometric and gravimetric analysis, the pyrolysis volatiles were characterized by different optical techniques. Absorption measurements showed a nearly featureless absorption in the ultraviolet spectral region with a continuously stronger absorption for shorter wavelengths. Using different excitation wavelengths, laser-induced fluorescence measurements revealed generally broad spectra in the spectral region from 300-500 nm, which are characteristic spectral signatures for larger hydrocarbons. The optical data were monitored at different times in the pyrolysis process of the particles and compared with the results from the mass spectrometric and gravimetric analysis. The sensitivity of the optical techniques for differentiation between specific molecules was rather low, although formaldehyde could be observed both in absorption and fluorescence spectra. Laser-induced fluorescence measurements were also made for two-dimensional visualization of the pyrolysis volatiles emitted from heated birchwood particles, indicating much higher flows along the fiber direction than across.