Thermal Conversion Characteristics of Molasses.

Agroindustrial biomass residues are considered potential feedstocks for renewable fuels and chemical production through processes such as thermal conversion. In this regard, thermal conversion characteristics of molasses, a byproduct from sugar production, have not been investigated. In this study, thermal conversion properties of molasses at temperatures of 700-900 °C have been studied using a single-particle reactor. Fuel swelling, combustion times, CO gas yields and gasification reactivities, and NO emissions and release of K and Cl during combustion and gasification were the thermal conversion characteristics of the molasses studied. In addition, the melting behavior of molasses ash produced at 500 °C was assessed using FactSage thermodynamic modeling and differential scanning calorimetry-thermogravimetric analysis measurements. Results of the molasses thermal conversion properties were compared with those of vinasse and black liquor samples from the integrated sugar-ethanol mill and soda pulping of hardwood, respectively. The results show that the molasses droplets had the least swelling tendency and the longest combustion time in the temperature range used, suggesting a lower conversion rate of molasses in an industrial boiler than the vinasse and black liquor. Moreover, at temperatures relevant for industrial gasification processes, that is, ≥800 °C, the gasification rates of molasses were lower than those of the vinasse and black liquor, probably owing to the lower total concentration of catalytic alkali and alkaline earth metals in the molasses. The release of K and Cl to a high degree from molasses during combustion and gasification and the low melting temperature of molasses ash make it a challenging fuel to utilize using the current thermal conversion technologies. Nevertheless, a black liquor recovery boiler type with a simpler (or an oxidizing) lower furnace than that of a black liquor recovery boiler and an entrained flow gasifier of the type demonstrated for black liquor may be potential options for the production of energy and recovery of inorganic chemicals from molasses.

Understanding the Interaction of Potassium Salts with an Ilmenite Oxygen Carrier Under Dry and Wet Conditions.

This study describes how potassium salts representative of those in bio ash affect the reactivity of the oxygen carrier ilmenite under moist and dry conditions. Ilmenite is a bench-mark oxygen carrier for chemical-looping combustion, a technique that can separate CO2 from flue gases with minimal energy penalty. Different potassium salts were mixed with ilmenite to a concentration of 4 wt % potassium. The salts used were K2CO3, K2SO4, KCl, and KH2PO4. Experiments were performed at 850 °C under alternately oxidizing and reducing conditions in a dry atmosphere or in the presence of steam. Analyses of the oxygen carrier regarding changes in reactivity, structure, and composition followed the exposures. This study showed that salts such as K2CO3, K2SO4, and KCl increase the reactivity of the ilmenite. For the samples mixed with KCl, most of the salt was evaporated. KH2PO4 decomposed into KPO3, forming layers around the ilmenite particles that lead to agglomeration. Additionally, the KPO3 layer was more or less nonpermeable for CO and decreased the reactivity toward H2 significantly in both dry and wet conditions. This decreased reactivity indicates that the concentration of phosphorus in biofuel may have a significant effect on oxygen carrier degradation. It was also observed that the presence of steam changed the chemistry drastically for the nonphosphorus-containing salts. Alkali salts may react with steam, forming volatile KOH that evaporates partly. KOH may also form K-titanates by reaction with the oxygen carrier, leading to segregation of iron and titanium phases in the ilmenite.

NO and SO2 emissions from combustion of raw and torrefied biomasses and their blends with lignite.

The impact of torrefaction on the NO and SO2 emissions from combustion of biomass was investigated. Combustion experiments were carried out with two torrefied biomass fuels, i.e., poultry litter and olive tree pruning and their blends with lignite using a bench scale single particle reactor. For comparison, NO and SO2 emissions from tests with untorrefied biomasses and their blends with lignite were also investigated. The total release of SO2 and NO for each fuel was determined at three different temperatures: 900, 1000, and 1100 °C. The NO release from the untorrefied biomasses was found to be lower than those from torrefied biomasses, despite their higher fuel- N content. In case of co-combustion of both raw and torrefied biomass with lignite, the NO release was lower than the anticipated one. On the other hand, in the co-combustion experiments, blends with torrefied biomass showed a larger reduction in SO2 release than the blends with raw biomass. The study revealed that the SO2 emissions from blends are not proportional to the mixing ratio of the fuels and to the emissions properties of the respective fuels. No clear correlation was detected between the NOx emissions and fuel-N content. In addition to the NO and SO2 emissions, the sintering propensity of the ash residue were investigated using scanning electron microscopy (SEM).

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.

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.