Characterization of biochar of pine pellet

Journal of Thermal Analysis and Calorimetry - Recently, biochar was introduced as a bioadsorbent material to remove various contaminants in effluents, such as pigments, dyes, heavy metals,...     

Study of the pyrolysis liquids obtained from different sewage sludge

Pyrolysis of sewage sludge in fluidized bed to produce bio-oil is under study as a useful way to valorise this waste. Sewage sludge is the waste produced in the wastewater treatment plants. Its composition may change due to the origin and to the non-standardized treatments in the wastewater treatment plants. The pyrolysis of three samples of anaerobically digested sewage sludge obtained from three different urban wastewater treatment plants was studied in this work. The organic and inorganic matter composition, and the volatile and ash content of these sewage sludge samples were different. The influence of these parameters on the pyrolysis product distribution and on some characteristics of these products was studied. It was determined that the ash content of the raw material had an enormous influence on the sewage sludge pyrolysis. An increase in the ash content of the sewage sludge caused an increase in the gas yield and a decrease in the liquid and the solid yield with the operational conditions studied. The increase of the volatile content of the sewage sludge samples caused an increase in the liquid yield. The H₂ proportion was the most influenced non-condensable gas. It increased significantly with the ash content. The viscosity of the pyrolysis oils decreased when the ash content augmented. On the other hand, the water content depended on the organic composition of the sewage sludge samples. The chemical composition of the pyrolysis oils was also affected by the sewage sludge ash content above all the proportion of polyaromatic hydrocarbons and nitrogen-containing aromatic compounds. These compound groups increased with the augment of the sewage sludge ash content. The oxygen-containing aliphatic compounds and the steroids decreased with the ash content, although its proportion in the sewage sludge liquid was also influenced by the organic matter composition of the sewage sludge samples.     

Thermal self-sustainability of biochar production by pyrolysis

The pyrolysis of several agricultural and biofuel production residues (grape residues, sugarcane residues, dried distiller's grain, palm oil residues, apple pomace and forestry residue) has been carried out in a pilot bubbling fluidized bed pyrolyzer operating under a range of temperature from 300 to 600 °C and two vapor residence times (2 and 5 s), with the aim of determining their pyrolysis behavior including products yields and heat balance. The composition of the product gases was determined, from which their heating value was calculated. The liquid bio-oil was recovered with cyclonic condensers. The thermal sustainability of the pyrolysis process was estimated by considering the energy contribution of the product gases and of the liquid bio-oil in relation to the pyrolysis heat requirements. The most promising biomass feedstocks for the sustainable production of biochar were indentified. Furthermore, this study presented the char yield in relation to the excess heat that could be obtained by combusting the gas and bio-oil coproducts of biochar production, as functions of pyrolysis temperature and vapor residence time.     

Characterization of the different fractions obtained from the pyrolysis of rope industry waste

A study of the possibilities of pyrolysis for recovering wastes of the rope's industry has been carried out. The pyrolysis of this lignocellulosic residue started at 250 °C, with the main region of decomposition occurring at temperatures between 300 and 350 °C. As the reaction temperature increased, the yields of pyrolyzed gas and oil increased, yielding 22 wt.% of a carbonaceous residue, 50 wt.% tars and a gas fraction at 800 °C. The chemical composition and textural characterization of the chars obtained at various temperatures confirmed that even if most decomposition occurs at 400 °C, there are some pyrolytic reactions still going on above 550 °C. The different pyrolysis fractions were analyzed by GC–MS; the produced oil was rich in hydrocarbons and alcohols. On the other hand, the gas fraction is mainly composed of CO₂, CO and CH₄. Finally, the carbonaceous solid residue (char) displayed porous features, with a more developed porous structure as the pyrolysis temperature increased.     

Thermal analysis of soil amended with sewage sludge and biochar from sewage sludge pyrolysis

The main objective of the present study is to study the behaviour of sewage sludge and biochar from sewage sludge pyrolysis after addition to soil in a context of a temperate agricultural soil. For this, an incubation experiment was designed during 200 days. Carbon mineralization of soil amended with sewage sludge and biochar at two different rates (4 and 8 wt%) was evaluated. Differential thermal analysis, thermogravimetry and the first derivate of the TG were performed in oxidizing conditions on soil samples before and after incubation. Biochar obtained from sewage sludge pyrolysis at 500 °C was more stable in soil than original sewage sludge. After incubation experiment, the reduction of soil organic matter content was significantly lower in soil amended with biochar than in soil amended with sewage sludge. The thermostability index WL₃/WL₂ decreases after incubation in soil amended with biochar, however it increases in case of soil treated with sewage sludge.     

钾对松木热解特性影响实验研究

采用管式炉热解实验装置对浸渍K2CO3松木进行直接热解,并将松木热解气通过含钾石英砂层、含钾焦层以模拟钾对热解气体反应的影响。结果表明,松木中浸渍K后会促进热解固体焦生成,提高H2/CO比,低温下K会降低液相产率、提高气相产率,而热解温度较高时则使气体产率下降、液体产率提高。松木热解气经过含K石英砂后发生催化裂解,液体产率降低,CO、CO2和H2产量上升。松木焦也可以催化裂解焦油,使气体产物增加,H2和CO2产量提高,CO、CH4和C2产量降低。K与松木焦共同作用,不仅使焦油发生裂解而且促进更多焦参与气固反应。钾对松木热解作用是通过对松木的直接热解、对气体中间产物再反应的均相催化及对固体焦气化的非均相催化等复杂过程实现的。     

Thermal analysis of the combustion of charcoals from Eucalyptus dunnii obtained at different pyrolysis temperatures

DSC and TG/DTA were used to study charcoals obtained from eucalyptus wood at different pyrolysis temperatures, as well as the exchanged energy, and the transformations involved during the pyrolysis process. Charcoals DSC curves showed two exothermic peaks, at ~610 and ~750 K. The first peak was squashed for those charcoals obtained at higher final pyrolysis temperatures, and it disappeared in the charcoals obtained at 873 and 923 K. The second peak intensity increased and its location changed at the higher temperatures. Charcoal characterization showed a rise of heat values with the pyrolysis temperature.     

Effect of pyrolysis conditions on the properties of carbonaceous nanofibers obtained from freeze-dried cellulose nanofibers

Carbonaceous nanofibers (CsNFs) were produced by pyrolysis of cellulose nanofibers synthesised from wood pulp using a top-down approach. The effects of heat treatment conditions on the thermal, morphological, crystal and chemical properties of the CsNFs were investigated using TGA, SEM, XRD and FT-IR, respectively. The results showed that heat treatment conditions around the thermal decomposition temperature of cellulose greatly influence the morphology of resulting materials. Slow heating rates (1 °C/min) between 240 and 400 °C as well as prolonged isothermal heat treatment (17 h) at 240 °C were necessary to avoid destruction of the original fibrous morphology in carbonized nanofibers. On the other hand, such heat treatment had little effect on micron sized fibers. The optimized heat treatment conditions led to the release of oxygen and hydrogen from cellulose before thermal breakdown of glycosidic rings, which in turn prevented depolymerization and tar formation, resulting in the preservation of the fibrous morphology.     

Characterization of slow pyrolysis oil obtained from linseed (Linum usitatissimum L.)

This study presents the characterization of pyrolysis oil obtained from linseed (Linum usitatissimum L.) produced by slow pyrolysis in the maximum yield. The pyrolysis oil was analyzed to determine its elemental composition and calorific value. The chemical composition of the pyrolysis oil and fractions were investigated using chromatographic and spectroscopic techniques (¹H NMR, IR, and GC). The chemical class composition of the oil was determined by liquid column chromatographic fractionation. The oil was separated into pentane soluble and insoluble fractions by using pentane. The column was eluted successively with n-pentane, toluene and methanol to yield aliphatic, aromatic and polar fractions, respectively. The results of the adsorption chromatography of the oil showed that the pyrolysis oil consists of 88 wt% n-pentane soluble. The aliphatic, aromatic and polar fractions of oils obtained in slow pyrolysis are 30, 34, 36 wt%, respectively. The aliphatic and aromatic subtraction make up ∼64 wt% in slow pyrolysis oil. This seems to be more appropriate for the production of hydrocarbons and chemicals.     

Quality variations of poultry litter biochar generated at different pyrolysis temperatures

Producing biochar and biofuels from poultry litter (PL) through slow pyrolysis is a farm-based, value-added approach to recycle the organic waste. Experiments were conducted to examine the effect of pyrolysis temperature on the quality PL biochar and to identify the optimal pyrolysis temperature for converting PL to agricultural-use biochar. As peak pyrolysis temperature increased incrementally from 300 to 600 °C, biochar yield, total N content, organic carbon (OC) content, and cation exchange capacity (CEC) decreased while pH, ash content, OC stability, and BET surface area increased. The generated biochars showed yields 45.7–60.1% of feed mass, OC 325–380 g kg⁻¹, pH 9.5–11.5, BET surface area 2.0–3.2 m² g⁻¹, and CEC 21.6–36.3 cmol_c kg⁻¹. The maximal transformation of feed OC into biochar recalcitrant OC occurred at 500 °C, yet 81.2% of the feed N was lost in volatiles at this temperature. To produce agricultural-use PL biochar, 300 °C should be selected in pyrolysis; for carbon sequestration and other environmental applications, 500 °C is recommended.     

Kinetics of pyrolysis and combustion of pine needles and cones

A wide kinetic study has been carried out under different conditions in TG and TG–MS for each material, at different operating conditions. Runs were carried out at three different atmospheres: N₂, N₂:O₂ 4:1 and N₂:O₂ 9:1. In addition to the dynamic runs carried out at constant heating rate, other runs were performed in an isothermal regime (constant heating rate until the set temperature is reached and then the set temperature is maintained constant).In addition, a study of the thermal decomposition for both materials was also carried out in a dynamic run using TG–MS in order to observe the evolution of the major compounds and to discuss the information that could be obtained.From the overall analysis of the data, schemes of reactions and kinetic values were calculated by integration of the differential equations and minimizing the squared differences between the experimental and calculated values. It is important to emphasise that the same set of parameters is proposed for the runs for each material, and depends on neither the heating rate in dynamic runs nor whether the run is carried out in a dynamic or isothermal mode.     

Laboratory-scale production of biofuel pellets from electron beam treated Scots pine (Pinus silvestris L.) sawdust

The effect of electron beam (EB) treatment on pine sawdust used as raw material for fuel pellets was studied. Dry sawdust was EB treated at different dosage levels up to 100 kGy. The effect of EB treatment on fatty and resin acid composition was studied for different dosage levels and compared to untreated sawdust. Pellets were pressed in a laboratory single pellet press unit according to a D-optimal, response surface modeling (RSM) experimental design, where sawdust moisture content and die temperature were varied independently for EB treatment dosages of 0, 18.2 and 48.9 kGy. The responses of the designed experiment were density and strength for the produced pellets.The results showed that the free fatty and resin acid content in the sawdust initially decreased with increasing EB doses but at the highest EB doses it increased. The total content of extractives however initially increased and then decreased with increasing EB dose. Pellets made of EB treated sawdust had a significantly (at 95% confidence level) higher density and compressive strength than pellets made from untreated sawdust. EB treated sawdust behaved similarly to stored (mature) sawdust as a pellet raw material. Thus, EB treatment opens the possibility for controlled ageing (maturation) of pellet raw materials.     

Cadmium removal from aqueous solution by biochar obtained by co-pyrolysis of sewage sludge with tea waste

Resource utilization is a critical pathway for sustainable solid waste treatment. Biochar was prepared from the co-pyrolysis of sewage sludge and tea waste. Brunauer–Emmett–Teller measurement, scanning electron microscopy and Fourier transform infrared analysis were employed to characterize the biochar. Then, the interface behavior between biochar and Cd from aqueous solution was investigated. The effect of adsorbent dose and pH on Cd adsorption was evaluated. Adsorption kinetics and the adsorption isotherm were studied, and the adsorption mechanism was explored. The results showed that the suitable adsorbent dose was 4 g L^?1 and the optimal pH of the Cd solution remained at 6.0. Cadmium sorption on the biochar could be well described by the pseudo-second order kinetic model (R ² > 0.98). The adsorption process was described using the Langmuir (R ² > 0.86), Freundlich (R ² > 0.86), Temkin (R ² > 0.84) and Dubinin–Radushkevich (R ² > 0.86) isotherm models. The proportion of organic constituents in biochar was 69.2–72.4%. Minerals that originated in biochar played an important role during the Cd adsorption process, and the contribution of minerals accounted for 27.6–30.8% of the total adsorption. The main mechanism of the Cd adsorption process by biochar involved ion exchange, surface complexation, electrostatic interaction, surface co-precipitation, and other mechanisms. Therefore, biochar created by the co-pyrolysis of sewage sludge and tea waste could be used as an adsorbent for the removal of metal ions from contaminated water.     

The effect of chemical activation method on properties of activated carbons obtained from pine cones

A method for obtaining carbonaceous adsorbents from pine cones by chemical activation with NaOH is described. Activated carbons were obtained by two methods of activation (physical mixing and impregnation) and two variants of thermal treatment. It has been shown that pine cones can be successfully used as cheap precursor of carbonaceous adsorbents of well-developed surface area, large pore volume and good sorption properties. All activated carbon samples obtained show strongly microporous structure and surface of acidic character. The best physicochemical properties and greatest sorption capacity towards iodine were found for the carbon samples obtained by physical mixing of the precursor with the activating agent and then subjected to thermal activation at 600°C.     

Aromatics and phenols from catalytic pyrolysis of Douglas fir pellets in microwave with ZSM-5 as a catalyst

Microwave assisted catalytic pyrolysis was investigated to convert Douglas fir pellets to bio-oils by a ZSM-5 zeolite catalyst. A central composite experimental design (CCD) was used to optimize the catalytic pyrolysis process. The effects of reaction time, temperature and catalyst to biomass ratio on the bio-oil, syngas, and biochar yields were determined. GC/MS analysis results showed that the bio-oil contained a series of important and useful chemical compounds. Phenols, guaiacols, and aromatic hydrocarbons were the most abundant compounds which were about 50–82% in bio-oil depending on the pyrolysis conditions. Comparison between the bio-oils from microwave pyrolysis with and without catalyst showed that the catalyst increased the content of aromatic hydrocarbons and phenols. A reaction pathway was proposed for microwave assisted catalyst pyrolysis of Douglas fir pellets.     

Electrochemical devices obtained from biochar: Advances in renewable and environmentally-friendly technologies applied to analytical chemistry

Biochar is the carbon-rich material produced from organic feedstock such as agricultural wastes and municipal solid waste in limited oxygen atmosphere and under certain thermal combustion. Due to its high carbon content, high cation exchange capacity, large surface and stability structure, it has been applied in different field of knowledge. In relation to environment analytical chemistry the studies about biochar majorly focus in degradation of contaminants and soil and water remediation. However, due to its excellent electrical conductivity, biochar has been also applied to the manufacture of sensitive, robust, efficient and inexpensive devices applied to supercapacitor-based energy storage and chemically modified electrodes or sensors. Therefore, this review describes about obtention, modification and characterization of biochar as well as the pertinent aspects of electrochemical devises based on biochar and a general discussion about the environmental concern of biochar, challenges and prospects.     

Energy levels of small titanium oxide clusters obtained from SCF calculations

The energy levels of small titanium oxide clusters [(TiO₂)₂, and (TiO₂H)₃, and (TiO₂H)₂] have been calculated using ab initio SCF methods. Both crystal and relaxed geometries have been considered. Systematic changes in the valencelevel structure resulting from geometry relaxation are found, which may be related to band-gap changes experimentally observed for small titanium oxide particles. In addition, a Ti? OH local surface state is found to be well described within a limited cluster model. © 1994 John Wiley & Sons, Inc.     

Production of char from vacuum pyrolysis of South-African sugar cane bagasse and its characterization as activated carbon and biochar

The potential of vacuum pyrolysis to convert sugar cane bagasse into char materials for wastewater treatment and soil amendment is the focus of this research paper. Vacuum pyrolysis produces both bio-oil and char in similar quantities. Vacuum pyrolysis has the potential to produce high quality chars for wastewater treatment and soil amendment directly during the conversion process, with no further upgrading required. In the present study, chars with the required porous structure was obtained directly from the vacuum pyrolysis process, making it very efficient as adsorbent both in terms of methylene blue (MB) adsorption with a N₂-BET surface area of 418 m² g⁻¹. Further steam activation of the chars benefited the development of meso- and macroporosity, although this upgrading step was not essential to achieve the required performance of char as an MB adsorbent. The development of large pores during the vacuum pyrolysis favored physisorption of MB, rather than chemisorption. The chemical nature of the vacuum pyrolysis char resulted in a slightly acidic surface (pH 6.56). The biochar from vacuum pyrolysis can be considered as a highly beneficial soil amendment, as it would enhance soil nutrient and water holding capacity, due to its high cation exchange capacity (122 cmol_c kg⁻¹) and high surface area. It is also a good source of beneficial plant macro- and micronutrients and contains negligible levels of toxic elements.