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.

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.

Thermal treatment of solid residues from WtE units: a review.

Thermal treatment methods of bottom ash, fly ash and various types of APC (air pollution control) residues from waste-to-energy plants can be used to obtain environmentally stable material. The thermal treatment processes are meant to reduce the leachability of harmful residue constituents, destroy toxic organic compounds, reduce residue volume, and produce material suitable for utilization. Fly ash and APC residues often have high levels of soluble salts, particularly chlorides, metals such as cadmium, lead, copper and zinc, and trace levels of organic pollutants such as dioxins and furans. Different thermal treatment methods can be used to either decompose or stabilize harmful elements and compounds in the ash, or separate them from the ash to get a material that can be safely stored or used as products or raw materials. In the present paper, thermal treatment methods, such as sintering, vitrification, and melting have been reviewed. In addition to a review of the scientific literature, a survey has been made of the extensive patent literature in the field.

The presence of zinc in Swedish waste fuels.

Zinc (Zn) is a chemical element that has gained more attention lately owing to its possibility to form corrosive deposits in large boilers, such as Waste-to-Energy plants. Zn enters the boilers in many different forms and particularly in waste, the amount of Zn is hard to determine due to both the heterogeneity of waste in general but also due to the fact that little is yet published specifically about the Zn levels in waste. This study aimed to determine the Zn in Swedish waste fuels by taking regular samples from seven different and geographically separate waste combustion plants over a 12-month period. The analysis shows that there is a relation between the municipal solid waste (MSW) content and the Zn-content; high MSW-content gives lower Zn-content. This means that waste combustion plants with a higher share of industrial and commercial waste and/or building and demolition waste would have a higher share of Zn in the fuel. The study also shows that in Sweden, the geographic location of the plant does not have any effect on the Zn-content. Furthermore, it is concluded that different seasons appear not to affect the Zn concentrations significantly. In some plants there was a clear correlation between the Zn-content and the content of other trace metals.

Determination of fossil carbon content in Swedish waste fuel by four different methods.

This study aimed to determine the content of fossil carbon in waste combusted in Sweden by using four different methods at seven geographically spread combustion plants. In total, the measurement campaign included 42 solid samples, 21 flue gas samples, 3 sorting analyses and 2 investigations using the balance method. The fossil carbon content in the solid samples and in the flue gas samples was determined using (14)C-analysis. From the analyses it was concluded that about a third of the carbon in mixed Swedish waste (municipal solid waste and industrial waste collected at Swedish industry sites) is fossil. The two other methods (the balance method and calculations from sorting analyses), based on assumptions and calculations, gave similar results in the plants in which they were used. Furthermore, the results indicate that the difference between samples containing as much as 80% industrial waste and samples consisting of solely municipal solid waste was not as large as expected. Besides investigating the fossil content of the waste, the project was also established to investigate the usability of various methods. However, it is difficult to directly compare the different methods used in this project because besides the estimation of emitted fossil carbon the methods provide other information, which is valuable to the plant owner. Therefore, the choice of method can also be controlled by factors other than direct determination of the fossil fuel emissions when considering implementation in the combustion plants.

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 vitro behaviour of three biocompatible glasses in composite implants.

Poly(L,DL-lactide) composites containing filler particles of bioactive glasses 45S5 and S53P4 were compared with a composite containing a slowly dissolving glass S68. The in vitro reactivity of the composites was studied in simulated body fluid, Tris-buffered solution, and phosphate buffered saline. The high processing temperature induced thermal degradation giving cavities in the composites containing 45S5 and S53P4, while good adhesion of S68 to the polymer was observed. The cavities partly affected the in vitro reactivity of the composites. The degradation of the composites containing the bioactive glasses was faster in phosphate buffered saline than in the two other solutions. Hydroxyapatite precipitation suggesting bone tissue bonding capability was observed on these two composites in all three solutions. The slower dissolution of S68 glass particles and the limited hydroxyapatite precipitation suggested that this glass has potential as a reinforcing composition with the capability to guide bone tissue growth in biodegradable polymer composites.

Comparing the greenhouse gas emissions from three alternative waste combustion concepts.

Three alternative condensing mode power and combined heat and power (CHP) waste-to-energy concepts were compared in terms of their impacts on the greenhouse gas (GHG) emissions from a heat and power generation system. The concepts included (i) grate, (ii) bubbling fluidised bed (BFB) and (iii) circulating fluidised bed (CFB) combustion of waste. The BFB and CFB take advantage of advanced combustion technology which enabled them to reach electric efficiency up to 35% and 41% in condensing mode, respectively, whereas 28% (based on the lower heating value) was applied for the grate fired unit. A simple energy system model was applied in calculating the GHG emissions in different scenarios where coal or natural gas was substituted in power generation and mix of fuel oil and natural gas in heat generation by waste combustion. Landfilling and waste transportation were not considered in the model. GHG emissions were reduced significantly in all of the considered scenarios where the waste combustion concepts substituted coal based power generation. With the exception of condensing mode grate incinerator the different waste combustion scenarios resulted approximately in 1 Mton of fossil CO(2)-eq. emission reduction per 1 Mton of municipal solid waste (MSW) incinerated. When natural gas based power generation was substituted by electricity from the waste combustion significant GHG emission reductions were not achieved.

Antibacterial effects and dissolution behavior of six bioactive glasses.

Dissolution behavior of six bioactive glasses was correlated with the antibacterial effects of the same glasses against sixteen clinically important bacterial species. Powdered glasses (<45 microm) were immersed in simulated body fluid (SBF) for 48 h. The pH in the solution inside the glass powder was measured in situ with a microelectrode. After 2, 4, 27, and 48 h, the pH and concentration of ions after removing the particles and mixing the SBF were measured with a normal glass pH electrode and ICP-OES. The bacteria were cultured in broth with the glass powder for up to 4 days, after which the viability of the bacteria was determined. The antibacterial effect of the glasses increased with increasing pH and concentration of alkali ions and thus with increased dissolution tendency of the glasses, but it also depended on the bacterium type. The changes in the concentrations of Si, Ca, Mg, P, and B ions in SBF did not show statistically significant influence on the antibacterial property. Bioactive glasses showed strong antibacterial effects for a wide selection of aerobic bacteria at a high sample concentration (100 mg/mL). The antibacterial effects increased with glass concentration and a concentration of 50 mg/mL (SA/V 185 cm(-1)) was required to generate the bactericidal effects. Understanding the dissolution mechanisms of bioactive glasses is essential when assessing their antibacterial effects.

Bioceramic inlays do not improve mechanical incorporation of grit-blasted titanium stems in the proximal sheep femur.

The aim of the present study was to determine, if bioactive glass (BG) surface inlays improve osseointegration of titanium implants in the proximal femur of adult sheep. In simulation of uncemented primary stems (nine animals), only the proximal part of the implants was grit-blasted and three surface slots of the grit-blasted region were filled with sintered BG microspheres. Primary stems were implanted using press-fit technique. In revision stem simulation (eight animals), grit-blasting was extended over the whole implant and seven perforating holes of the stem were filled by sintered BG granules. Revision stems were implanted with a mixture of autogenous bone graft and BG granules. Comparison with solid partially or fully grit-blasted control stems implanted in the contralateral femurs was performed in the primary and revision stem experiments at 12 and 25 weeks, respectively. Implant incorporation was evaluated by torsional failure testing and histomorphometry. Only one-third of the primary stems anchored mechanically to bone. The revision stems incorporated better and the BG inlays of the revision stems showed ingrowth of new bone. However, there were no significant differences in the torsional failure loads between the stems with BG inlays and the control stems. In conclusion, surface BG inlays gave no measurable advantage in mechanical incorporation of grit-blasted titanium implants. Overall, the proximal sheep femur, characterized by minimal amount of cancellous bone and the presence of adipocytic bone marrow, seemed to present compromised bone healing conditions.

In situ pH within particle beds of bioactive glasses.

The in vitro behavior of three bioactive glasses with seven particle size distributions was studied by measuring the in situ pH inside the particle beds for 48h in simulated body fluid (SBF). After immersion, the surface of the particles was characterized with a field emission scanning electron microscope equipped with an energy-dispersive X-ray analyzer. In addition, the results were compared with the reactions of the same glasses formed as plates. A similar trend in pH as a function of immersion time was observed for all systems. However, the pH inside the particle beds was markedly higher than that in the bulk SBF of the plates. The pH decreased as power functions with increasing particle size, i.e. with decreasing surface area. The in vitro reactivity expressed as layer formation strongly depended on the particle size and glass composition. The average thickness of the total reaction layer decreased with the increase in sample surface area. Well-developed silica and calcium phosphate layers typically observed on glass plates could be detected only on some particles freely exposed to the solution. No distinct reaction layers were observed on the finest particles, possibly because the layers spread out on the large surface area. Differences in the properties of the bulk SBF and the solution inside the particle bed were negligible for particles larger than 800microm. The results enhance our understanding of the in vitro reactions of bioactive glasses in various product forms and sizes.

Pyrolysis of softwood carbohydrates in a fluidized bed reactor.

In the present work pyrolysis of pure pine wood and softwood carbohydrates, namely cellulose and galactoglucomannan (the major hemicellulose in coniferous wood), was conducted in a batch mode operated fluidized bed reactor. Temperature ramping (5 degrees C/min) was applied to the heating until a reactor temperature of 460 degrees C was reached. Thereafter the temperature was kept until the release of non-condensable gases stopped. The different raw materials gave significantly different bio-oils. Levoglucosan was the dominant product in the cellulose pyrolysis oil. Acetic acid was found in the highest concentrations in both the galactoglucomannan and in the pine wood pyrolysis oils. Acetic acid is most likely formed by removal of O-acetyl groups from mannose units present in GGM structure.

Antibacterial effect of bioactive glasses on clinically important anaerobic bacteria in vitro.

Bioactive glasses (BAGs) of different compositions have been studied for decades for clinical use and they have found many dental and orthopaedic applications. Particulate BAGs have also been shown to have antibacterial properties. This large-scale study shows that two bioactive glass powders (S53P4 and 13-93) and a sol-gel derived material (CaPSiO II) have an antibacterial effect on 17 clinically important anaerobic bacterial species. All the materials tested demonstrated growth inhibition, although the concentration and time needed for the effect varied depending on the BAG. Glass S53P4 had a strong growth-inhibitory effect on all pathogens tested. Glass 13-93 and sol-gel derived material CaPSiO II showed moderate antibacterial properties.

Influence of pressure on pyrolysis of black liquor: 2. Char yields and component release.

This is the second in a series of papers concerning the behavior of black liquor during pyrolysis at elevated pressures. Two industrial black liquors were pyrolyzed under pressurized conditions in two laboratory-scale devices, a pressurized single-particle reactor and a pressurized grid heater. Temperatures ranging between 650 and 1100 degrees C and pressures in the range 1-20 bar were studied. Char yields were calculated and based on analysis of some of the chars the fate of carbon, sodium, potassium and sulfur was determined as a function of pyrolysis pressure. At temperatures below 800 degrees C little variation in char yield was observed at different pressures. At higher temperatures char yield increased with pressure due to slower decomposition of sodium carbonate. For the same reason, sodium release decreased with pressure. Sulfur release, however, increased with pressure primarily because there was less opportunity for its capture in the less-swollen chars.

Influence of pressure on pyrolysis of black liquor: 1. Swelling.

This is the first of two papers concerning the behavior of black liquor during pyrolysis under pressurized conditions. Two industrial kraft liquors were pyrolyzed in a laboratory-scale pressurized single particle reactor and a pressurized grid heater at temperatures ranging from 650 to 1100 degrees C and at pressures between 1 and 20 bar. The dimensions of the chars produced were measured and the specific swollen volume was calculated. Swelling decreased roughly logarithmically over the pressure range 1-20 r. An expression is developed to predict the specific swollen volume at elevated pressure when the volume at 1 bar is known. The bulk density of the char increased with pressure, indicating that liquors will be entrained less easily at higher pressures.

Biologic significance of surface microroughing in bone incorporation of porous bioactive glass implants.

A novel chemical etching method was recently developed to create a controlled microrough surface on porous bioactive glass implants. Our earlier in vitro studies showed enhanced attachment of osteoblast-like MG63 cells on a microrough bioactive glass surface. The purpose of our current study was to confirm the in vivo significance of surface microroughening for bone bonding of bioactive glass. Porous bioactive glass cones made of sintered microspheres were surgically implanted in the anterior cortex of rabbit femurs. Peripheral quantitative computed tomography (pQCT), biomechanical push-out testing, histomorphometry, and electron microscopy (BEI-SEM) were used to analyze bone ingrowth and osseointegration at 7, 10, 14, 28, 56, and 84 days after implantation. The results showed that microroughening of the bioactive glass surface significantly enhanced the bone-bonding response of the biomaterial. The positive response was seen in one of the three bioactive glass compositions studied. The affinity index of new bone on the glass surface was significantly (p = 0.02) increased with a trend (p = 0.10) toward improved mechanical incorporation. New bone formation was dependent on the glass composition, and it was found to occur not only through the mechanism of bone ingrowth but also based on in situ osteogenesis within implant interstices. Based on these results, the procedure of microroughening could enhance the osteopromotive properties of certain bioactive glass compositions.

Combustion and Gasification Properties of Plastics Particles.

The combustion and gasification behavior of the most common plastics is studied and compared with conventional fuels such as coal, peat, and wood. The aim is to give background data for finding the optimum conditions for co-combustion or co-gasification of a conventional fuel with a certain amount of plastic-derived fuel. Atmospheric or pressurized fluidized bed co-combustion of conventional fuels and plastics are considered to be promising future options. The plastics investigated were poly(ethylene) (PE), poly(propylene) (PP), poly(styrene) (PS), and poly(vinyl chloride) (PVC). Some of the samples had a print or color. The reference fuels were Polish bituminous coal, Finnish peat, and Finnish pine wood. PE, PP, and PS were found to burn like oil. The particles shrank to a droplet and burned completely during the pyrolysis stage, leaving no char. Printing and coloring left a small portion of ash. PVC was the only plastic that produced a carbonaceous residue, and its timescales for heating, devolatilization, and char burning were of the same order as those for peat and wood, and much shorter for the other plastics studied. An important result is that char from PVC contains less than 1% chlorine,99% hydrocarbon. The gasification rate of PVC char (at 1 bar and 25 bar) was of the same order as that of char from coal. Peat-char and wood-char were gasified an order of magnitude faster.