Nikolai DeMartini

Pyrolysis of pine and gasification of pine chars - influence of organically bound metals.

Pyrolysis of pine and gasification of pine chars was studied in this work, focusing on the influence of organically bound metals. Selective leaching of the major ash-forming elements in pine wood was performed with different acids, namely, nitric, sulfuric, hydrochloric and oxalic acids. No other major changes in the chemical composition of the biomass were observed except the removal of the metals. The effect of organically bound sodium, potassium, magnesium and calcium was studied in both pyrolysis and gasification. Removal of the metals had a positive effect on the pyrolysis, resulting in higher bio-oil, lower char and gas yields.

Measuring the concentration of carboxylic acid groups in torrefied spruce wood

Torrefaction is moderate thermal treatment (∼200-300°C) to improve the energy density, handling and storage properties of biomass fuels. In biomass, carboxylic sites are partially responsible for its hygroscopic. These sites are degraded to varying extents during torrefaction. In this paper, we apply methylene blue sorption and potentiometric titration to measure the concentration of carboxylic acid groups in spruce wood torrefied for 30min at temperatures between 180 and 300°C. The results from both methods were applicable and the values agreed well. A decrease in the equilibrium moisture content at different humidity was also measured for the torrefied wood samples, which is in good agreement with the decrease in carboxylic acid sites. Thus both methods offer a means of directly measuring the decomposition of carboxylic groups in biomass during torrefaction as a valuable parameter in evaluating the extent of torrefaction which provides new information to the chemical changes occurring during torrefaction.

In Situ Measurement Technique for Simultaneous Detection of K, KCl, and KOH Vapors Released during Combustion of Solid Biomass Fuel in a Single Particle Reactor:

A quantitative and simultaneous measurement of K, KCl, and KOH vapors from a burning fuel sample combusted in a single particle reactor was performed using collinear photofragmentation and atomic absorption spectroscopy (CPFAAS) with a time resolution of 0.2 s. The previously presented CPFAAS technique was extended in this work to cover two consecutive fragmentation pulses for the photofragmentation of KCl and KOH. The spectral overlapping of the fragmentation spectra of KCl and KOH is discussed, and a linear equation system for the correction of the spectral interference is introduced. The detection limits for KCl, KOH, and K with the presented measurement arrangement and with 1 cm sample length were 0.5, 0.1, and 0.001 parts per million, respectively. The experimental setup was applied to analyze K, KCl, and KOH release from 10 mg spruce bark samples combusted at the temperatures of 850, 950, and 1050 °C with 10% of O2. The combustion experiments provided data on the form of K vapors and their release during different combustion phases and at different temperatures. The measured release histories agreed with earlier studies of K release. The simultaneous direct measurement of atomic K, KCl, and KOH will help in the impact of both the form of K in the biomass and fuel variables, such as particle size, on the release of K from biomass fuels.

Sugarcane vinasse CO2 gasification and release of ash-forming matters in CO2 and N2 atmospheres.

Gasification of sugarcane vinasse in CO2 and the release of ash-forming matters in CO2 and N2 atmospheres were investigated using a differential scanning calorimetry and thermogravimetric analyzer (DSC-TGA) at temperatures between 600 and 800°C. The results showed that pyrolysis is the main mechanism for the release of the organics from vinasse. Release of ash-forming matters in the vinasse is the main cause for vinasse char weight losses in the TGA above 700°C. The losses are higher in N2 than in CO2, and increase considerably with temperature. CO2 gasification also consumes the carbon in the vinasse chars while suppressing alkali release. Alkali release was also significant due to volatilization of KCl and reduction of alkali sulfate and carbonate by carbon. The DSC measured thermal events during heating up in N2 atmosphere that correspond to predicted melting temperatures of alkali salts in the char.

Potential for thermochemical conversion of biomass residues from the integrated sugar-ethanol process - Fate of ash and ash-forming elements

In this work, potential for thermochemical conversion of biomass residues from an integrated sugar-ethanol process and the fate of ash and ash-forming elements in the process are presented. Ash, ash-forming elements, and energy flows in the process were determined using mass balances and analyses of eight different biomass samples for ash contents, elemental compositions, and heating values. The results show that the ash content increases from the sugarcane to the final residue, vinasse. The cane straw, which is left in the field, contains one-third of the energy and 25% of the K and Cl while the vinasse contains 2% of the energy and 40% of the K and Cl in the cane. K and Cl in biomass fuels cause corrosion and fouling problems in boilers and gasifiers. Over 85% of these elements in the straw are water soluble indicating that water leaching would improve it for utilization in thermochemical conversion.