Hydrothermal conversion of seaweeds in a batch autoclave

In this study, different seaweed species were gasified in supercritical water as biomass feedstock. The experimental conditions were 500 °C of temperature and 1 h of reaction time. The amount of gases, the gas compositions and the amount of water soluble compounds from gasification were determined. The coke yields were found to be significantly lower than those obtained with lignocellulosic and protein contained wastes. The gaseous species detected contain mainly hydrogen, methane and carbon dioxide. The hydrogen yields ranging between 11.8 and 16 g H₂/kg seaweed have been obtained. On the other hand, the methane yields were found to be in the range of 39 and 104 g CH₄/kg seaweed. The contents of aqueous phases were also determined using various analytical techniques. DOC (dissolved organic carbon) values of aqueous phases showed the high extent of gasification.     

Energetic analysis of gasification of biomass by partial oxidation in supercritical water

Partial oxidation gasification in supercritical water could produce fuel gases (such as H2, CO and CH4) and signif-icantly reduce the energy consumption. In this work, an energetic model was developed ...     

生物质超临界水部分氧化气化的能量过程分析(英文)

Partial oxidation gasification in supercritical water could produce fuel gases (such as H2, CO and CH4) and signif-icantly reduce the energy consumption. In this work, an energetic model was developed to analyze the partial oxidative gasification of biomass (glucose and lignin) in supercritical water and the related key factors on which gasification under autothermal condition depended upon. The results indicated that the oxidant equiva-lent ratio (ER) should be over 0.3 as the concern about energy balance but less than 0.6 as the concern about fuel gas production. Feedstocks such as glucose and lignin also had different energy recovery efficiency. For ma-terials which can be efficiently gasified, the partial oxidation might be a way for energy based on the combustion of fuel gases. Aromatic materials such as lignin and coal are more potential since partial oxidation could produce similar amount of fuel gases as direct gasification and offer additional energy. Energy recovered pays a key role to achieve an autothermal process. Keeping heat exchanger efficiency above 80%and heat transfer coefficient below 15 kJ·s?1 is necessary to maintain the autothermal status. The results also indicated that the biomass loading should be above 15%but under 20%for an autothermal gasification, since the increase of biomass loading could improve the energy supplied but decrease the efficiency of gasification and gaseous yields. In general, some specific conditions exist among different materials.     

Catalytic effects of NaOH and ZrO2 for partial oxidative gasification of n-hexadecane and lignin in supercritical water☆

Partial oxidative gasification of n-hexadecane (n-C₁₆) and organosolv-lignin (lignin) was studied by use of a batch type reactor in supercritical water: 673 K, 0.52 cm⁻³ of water density (40 MPa of water pressure at 673 K), and 0.3 of O/C ratio for the n-C₁₆ experiments; 673 K, 0.35 cm⁻³ of water density (30 MPa of water pressure at 673 K), and 1.0 of O/C ratio for the lignin experiments. The experiments without O₂ were also conducted for lignin (lignin decomposition). For all the cases (n-C₁₆ partial oxidation, lignin decomposition, lignin partial oxidation), NaOH or zirconia (ZrO₂) was added in the system as catalysts. Through n-C₁₆ studies, the catalytic effect of NaOH and ZrO₂ on partial oxidation in supercritical water were examined. In the case of lignin partial oxidation, we studied the possibility of partial oxidation in supercritical water for gasification technique of wastes. The yield of H₂ from n-C₁₆ and lignin with zirconia was twice as same as that without catalyst at the same condition. The H₂ yield with NaOH was 4 times higher than that without catalyst. Thus, a base catalyst has a positive effect on partial oxidation of n-C₁₆ and lignin to produce H₂. The catalytic effect of NaOH and ZrO₂ was found to be enhancement of decomposition of intermediate (aldehyde and ketone) into CO, through n-C₁₆ studies. In the case of lignin studies, the enhancement of decomposition of the carbonyl compounds by catalytic effect of NaOH and ZrO₂ inhibit char formation and promotes CO and thus H₂ formation.     

Prediction of the behaviors of H2S and HCl during gasification of selected residual biomass fuels by equilibrium calculation

H₂S and HCl released during biomass gasification can decrease the performance of high-temperature fuel cells in an Integrated Biomass Gasification Fuel Cell power-generating system. In this study, the behaviors of such poisonous gases during the gasification of different biomass fuels at various temperatures ranging from 673 to 1473 K were predicted using an equilibrium calculation approach. The predictions showed not only a difference in emission behaviors of HCl and H₂S among the biomass fuels, but also a low HCl emission (below 10 ppmv) for a few of the fuels at any temperature. In addition, the influence of biomass metal composition and gasification temperature on emission behavior was investigated by analyzing the distribution of chlorine and sulfur compounds and the phase diagram of selected elements such as silicon and aluminum. Finally, we suggest that the addition of a potassium-rich biomass to a potassium-poor biomass has the potential to reduce the HCl emission during gasification and then to maintain the HCl concentration in gas phase below the tolerance concentration of the fuel cells.     

Non-catalytic conversion of wheat straw,walnut shell and almond shell into hydrogen rich gas in supercritical water media

Agricultural wastes as lignocellulosic biomasses are known as the major resources of bioenergy. These valuable resources can be converted into useful environmental friendly fuels and chemicals. Wheat straw, walnut shell and almond shell are the main agricultural wastes in Kurdistan province, Iran. This study investigates the hydrogen-rich gas production via gasification of these biomasses in supercritical water media. Experiments were performed first, in the base case condition using a stainless steel batch micro reactor system. Then, the effect of reaction time on the total gas yield and yield of hydrogen, were investigated. It was seen that the total gas yields and gasification efficiencies increased by increasing the reaction time to 30 min and then the total gas yield was approximately remained constant. Among three used feed stocks, wheat straw with higher amount of cellulose and lower amount of lignin had the highest total gas and hydrogen yields in shorter reaction times. The maximum hydrogen yields of 7.25, 4.1 and 4.63 mmol per gram of wheat straw, almond shell and walnut shell occurred at 10, 15 and 20 min of reaction time, respectively.     

Study of a downdraft gasifier and externally fired gas turbine for olive industry wastes

Olive mill technology generates a variety of biomass wastes: olive pits/stones and remaining pomace resultant from olive oil extraction. Solid wastes are also generated during the pruning of olive trees (leaves and small branches). This renewable biomass could be a feasible option in gasification technology. Thermodynamic calculations evaluate the optimum operating parameters of a small scale gasification system. The product gas obtained from the downdraft gasifier has low calorific values: 4.35 MJ kg^− 1for exhausted pomace, and around 5.20 MJ kg^− 1for olive pits and leaves and prunings. The power system provides 70 kW_e and 150 kW_th with a biomass consumption of 80-85 kg h^− 1. Simulation results show the most important operating parameters are turbine inlet temperature (TIT), pressure ratio (Π) and hot side temperature difference of the heat exchanger (HTHE). High electric efficiency (20%) and overall efficiency (65%) are achievable with such a system.     

The study of reactions influencing the biomass steam gasification process☆

Steam gasification studies were carried out in an atmospheric fluidised bed. The gasifier was operated over a temperature range of 700-900 °C whilst varying a steam/biomass ratio from 0.4 to 0.85 w/w. Three types of forestry biomass were studied: Pinus pinaster (softwood), Eucalyptus globulus and holm-oak (hardwood). The energy conversion, gas composition, higher heating value and gas yields were determined and correlated with temperature, steam/biomass ratio, and species of biomass used. The results obtained seemed to suggest that the operating conditions were optimised for a gasification temperature around 830 °C and a steam/biomass ratio of 0.6-0.7 w/w, because a gas richer in hydrogen and poorer in hydrocarbons and tars was produced. These conditions also favoured greater energy and carbon conversions, as well the gas yield. The main objective of the present work was to determine what reactions were dominant within the operation limits of experimental parameters studied and what was the effect of biomass type on the gasification process. As biomass wastes usually have a problem of availability because of seasonal variations, this work analysed the possibility of replacing one biomass species by another, without altering the gas quality obtained.     

Co-gasification study of biomass mixed with plastic wastes

Fluidised bed steam gasification has proven to be a possible way of converting biomass and plastic undesirable wastes into fuel gases. The addition of plastics to pine wastes decreased CO content, but increased H₂ released, up to values of 50% (v/v). The highest gas yield obtained was 1.96 Nl/g daf for 98% of energy conversion, when 60% (w/w) of plastic was in the feedstock. The steam/waste mixture ratio seems to have a small effect on gas composition. Temperature is the parameter that most influenced gases composition. The rise of temperature favoured the formation of H₂ and decreased the formation of hydrocarbons, tars and char. At 885°C and in presence of 40% (w/w) of plastic, conversion to char was around 2%, whilst feedstock conversion to gas was around 90%. In this paper, the effect of experimental conditions on gasification process, with the aim of enhancing the gas production and improving its composition and energetic content was analysed.     

Behaviour of dolomite, olivine and alumina as primary catalysts in air-steam gasification of sewage sludge

Sewage sludge gasification assays were performed in an atmospheric fluidised bed reactor using air and air-steam mixtures as the gasifying agents. Dolomite, olivine and alumina are three well known tar removal catalysts used in biomass gasification processing. However, little information is available regarding their performance in sewage sludge gasification. The aim of the current study was to learn about the influence of these three catalysts in the product distribution and tar production during sewage sludge gasification. To this end, a set of assays was performed in which the temperature (750-850 °C), the in-bed catalyst content (0, 10 and 15 wt.%) and the steam-biomass ratio (SB) in the range of 0-1 were varied with a constant equivalence ratio (ER) of 0.3. The results were compared to the results from gasification without a catalyst. We show that dolomite has the highest activity in tar elimination, followed by alumina and olivine. In addition to improving tar removal, the presence of water vapour and the catalysts increased the content of H₂ in the gases by nearly 60%.     

The effect of steam on pyrolysis and char reactions behavior during rice straw gasification

Steam gasification of biomass can generate hydrogen-rich, medium heating value gas. We investigated pyrolysis and char reaction behavior during biomass gasification in detail to clarify the effect of steam presence. Rice straw was gasified in a laboratory scale, batch-type gasification reactor. Time-series data for the yields and compositions of gas, tar and char were examined under inert and steam atmosphere at the temperature range of 873-1173 K. Obtained experimental results were categorized into those of pyrolysis stage and char reaction stage. At the pyrolysis stage, low H₂, CO and aromatic tar yields were observed under steam atmosphere while total tar yield increased by steam. This result can be interpreted as the dominant, but incomplete steam reforming reactions of primary tar under steam atmosphere. During the char reaction stage, only H₂ and CO₂ were detected, which were originated from carbonization of char and char gasification with steam (C + H₂O→CO + H₂). It implies the catalytic effect of char on the water-gas shift reaction. Acceleration of char carbonization by steam was implied by faster hydrogen loss from solid residue.     

Low-temperature gasification of a woody biomass under a nickel-loaded brown coal char

Catalytic gasification of a woody biomass, Japanese cypress, was investigated under a prepared nickel-loaded brown coal (LY-Ni) char in a two-stage fixed-bed reactor. The nickel-loaded brown coal was prepared by ion-exchange method with a nickel loading rate of 8.3 wt.%. Nickel species dispersed well in the brown coal, and the LY-Ni char via devolatilization at 600 °C showed a great porous property with a specific surface area of 382 m² g^− 1.The LY-Ni char was confirmed to be quite active for the Japanese cypress volatiles gasification at a relatively low-temperature range from 450 to 650 °C. For example, at 550 °C, 16.6 times hydrogen gas and 6.3 times total gases were yielded from the catalytic steam gasification of Japanese cypress volatiles under the LY-Ni char, compared with the case of non-catalyst. The biomass tar decomposition showed a dependence on catalyst temperatures. When the catalyst temperature was higher than 500 °C, Japanese cypress tar converted much efficiently, high gas yields and high carbon balances were obtained.     

Coffee husks gasification using high temperature air/steam agent

Analyses made on the world's biomass energy potential show that biomass energy is the most abundant sustainable renewable energy. The available technical biomass energy potential surpasses the total world's consumption levels of petroleum oils, coal and natural gas. In order to achieve a sustainable harnessing of the biomass energy potential and to increase its contribution to the world's primary energy consumption, there is therefore a need to develop and sustain contemporary technologies that increase the biomass-to-energy conversion. One such technology is the high temperature air/steam gasification (HTAG) of biomass. In this paper we present findings of gasification experimental studies that were conducted using coffee husks under high temperature conditions. The experiments were performed using a batch facility, which was maintained at three different gasification temperatures of 900 °C, 800 °C, and 700 °C. The study findings exhibited the positive influence of high temperature on increasing the gasification process. Chars left while gasifying at 800 °C and 700 °C were respectively 1.5 and 2.4 times that for the case of 900 °C. Furthermore, increased gasification temperature led to a linear increment of CO concentration in the syngas for all gasification conditions. The effect was more pronounced for the generally poorly performing gasification conditions of N₂ and 2% oxygen concentration. When gasification temperature was increased from 700 °C to 900 °C the CO yield for the 2% O₂ concentration increased by 6 times and that of N₂ condition by 2.5 times. The respective increment for the 3% and 4% O₂ conditions were only twofold. This study estimated the kinetic parameters for the coffee husks thermal degradation that exhibited a reaction mechanism of zero order with apparent activation energy of 161 kJ/mol and frequency factor of 3.89 × 10⁴/min.     

Elucidation of the interaction among cellulose,xylan, and lignin in steam gasification of woody biomass

The reaction mechanism for gas and tar evolution in the steam gasification of cellulose, lignin, xylan, and real biomass (pulverized eucalyptus) was investigated with a continuous cross‐flow moving bed type differential reactor, in which tar and gases can be fractionated according to reaction time. In the steam gasification of real biomass, the evolution rates of water‐soluble tar (derived from cellulose and hemicelluloses) and water‐insoluble tar (derived from lignin) decrease with increasing reaction time. It was found that the evolution of water‐soluble tar occurs earlier than in the gasification of pure cellulose, indicating an interaction of the three components. The predicted yield of water‐insoluble tar is substantially less than that of real biomass. This implies that the evolution of tar from the lignin component of biomass is enhanced, compared with pure lignin gasification, by other components. The gas evolution rate from real biomass is similar to that predicted by the superposition of cellulose, lignin, and xylan. © 2008 American Institute of Chemical Engineers AIChE J, 2009     

The fate of fuel-nitrogen during gasification of biomass in a pressurised fluidised bed gasifier

The distribution of fuel-nitrogen in gases, tar and char from gasification of biomass in a pressurised fluidised bed gasifier was investigated. Four species of biomass: birch, Salix, Miscanthus and Reed canary grass were gasified at 0.4 MPa and 900 °C. Oxygen-enriched nitrogen was used as fluidising agent. As a reference, gasification of Daw Mill coal was also carried out under the same experimental conditions. The experimental results illustrate that both the nature of the original fuels and the chemical structure of the nitrogen in the fuel have influence on the distribution of fuel-nitrogen in gases (NH₃, HCN, NO), tar and char under the employed experimental conditions. The present work also shows that the types of nitrogen heterocyclic compounds (NHCs) in the tar from different kinds of biomass are the same and the major compound is pyridine. However, the distribution of the various NHCs in the tar from the four species of biomass varies: the higher the content of fuel-nitrogen, the higher the concentration of two-ring NHCs in the tar. An effective method for extracting NHCs from the acidic absorption of the product gas was introduced in the present work. The method makes use of solid phase extraction (SPE) by a silica-based C₁₈ tube to extract the NHCs which subsequently were analysed by gas chromatography (GC) with flame ionisation detection (FID). The recovery and reproducibility of the SPE technique for NHCs is discussed.     

Hydrothermal gasification of olive mill wastewater as a biomass source in supercritical water

In this study, the hydrothermal gasification of biomass in supercritical water is investigated. The work is of peculiar value since a real biomass, olive mill wastewater (OMW), is used instead of model biomass compounds. OMW is a by-product obtained during olive oil production, which has a complex nature characterized by a high content of organic compounds and polyphenols. The high content of organics makes OMW a desirable biomass candidate as an energy source. The hydrothermal gasification experiments for OMW were conducted with five different reaction temperatures (400, 450, 500, 550 and 600 °C) and five different reaction times (30, 60, 90, 120 and 150 s), under a pressure of 25 MPa. The gaseous products are mainly composed of hydrogen, carbon dioxide, carbon monoxide and C₁-C₄ hydrocarbons, such as methane, ethane, propane and propylene. Maximum amount of the gas product obtained is 7.71 mL per mL OMW at a reaction temperature of 550 °C, with a reaction time of 30 s. The gas product composition is 9.23% for hydrogen, 34.84% for methane, 4.04% for ethane, 0.84% for propane, 0.83% for propylene, 49.34% for carbon dioxide, and 0.88% for minor components such as n-butane, i-butane, 1-butene, i-butene, t-2-butene, 1,3-butadiene and nitrogen at this reaction conditions.     

Hydro-liquefaction of woody biomass in sub- and super-critical ethanol with iron-based catalysts

Hydro-liquefaction of a woody biomass (Jack pine powder) in sub-/super-critical solution of ethanol without and with iron-based catalysts (5 wt% FeS or FeSO₄) was investigated with a stainless steel micro-reactor (10 mL) at temperatures of 473-623 K and an initial pressure of hydrogen varying from 2.0 to 10.0 MPa. Without catalyst, the oil yields were in the range of 17% and 44%, depending on temperature, reaction time and initial pressure of hydrogen. With catalysts, the Oil yields significantly increased while the yields of solid residue and gases and water decreased. A high oil yield of 63% was obtained with FeSO₄ at 623 K and 5 MPa of H₂ for 40 min. The elemental analyses and GC/MS measurements for the Oils revealed that the liquid products have much higher heating values than the crude wood sample and phenolic compounds were dominant in the Oils, irrespective of whether or what catalyst was used.     

Kinetic study on the thermal degradation of a biomass and its compost: Composting effect on hydrogen production

Compost from vegetable residues is usually used as an organic amendment to soil; however, their thermal degradation characteristics show that it could be used as raw material in air gasification facilities. According to the obtained data, hydrogen production is positively affected by composting, increasing hydrogen concentration in the raw gas from 15.2 to 22.6 vol%. This effect is related with physicochemical changes that occur during thermophilic stage of composting. After this step it does not observes any progress on hydrogen production.On the other hand, in order to compare thermal degradation of a biomass (Leucaena leucocephala) and two composts with different maturation levels, non-isothermal thermogravimetric analysis (TGA) has been used. Under inert atmosphere, data have been adequately simulated assuming three fractions (hemicellulose, cellulose and lignin) in both biomass and composts. However, under air atmosphere we have used a simplified model that assume two components in biomass (holocellulose and lignin) and three in composts (including humic substances). Using nth-order kinetic equations to describe component degradations, we have calculated a set of kinetic parameters which do not differ of the reported for other lignocellulosic materials. This procedure allows obtaining an approximate composition of samples.     

Effect of alkali concentrations and operating conditions on agglomeration/defluidization behavior during fluidized bed air gasification

Biomass gasification plays an important role in finding a solution to the energy crisis, and the fluidized bed (FB) is recognized as an important technique for using biomass. However, this process significantly tends toward bed material agglomeration. Accordingly, the aim of this study is to emphasize the effects of operating conditions and different Na concentrations on agglomeration behavior during FB air gasification. Defluidization time decreases as Na concentration increases from 0.8 to 3%. Defluidization time decreases as temperature and the amount of bed materials increase. In addition, no significant change in the trend for this process occurs as the equivalence ratio increases. Adding CaO and Al₂O₃ can significantly prolong this process, and the inhibition level follows the sequence: Al₂O₃ > CaO. The same observations are noted during both incineration and air gasification in the FB at various operating conditions.     

Flaming pyrolysis model of the fixed bed cross draft long-stick wood gasifier

The future industrial development of biomass energy depends on the application of renewable energy technology in an efficient manner. Of all the competing technologies under biomass, gasifiers are considered to be one of most viable applications. The use of biomass fuel, especially biomass wastes, for distributed power production can be economically viable in many parts of the world through gasification of biomass. Since biomass, is a clean and renewable fuel, gasification gives the opportunity to convert biomass into clean fuel gas or synthesis gas for industrial uses. The preparation of feedstock for a gasifier requires time, energy and labour and this has been a setback for gasifier technology development. The present work is focused on gasification of long-stick wood as a feed material for gasifiers. This application makes reduction not only in the cost but also on the power consumption of feed material preparation. A 50 m³/h capacity gasifier was fabricated in the cross draft mode. The cross draft mode makes it possible to produce low tar content in producer gas. This cross draft mode operates with 180 W of blower supply for air to produce 10 kW of thermal output. The initial bed heights of the long-stick wood and charcoal are 58 cm and 48 cm respectively. Results were obtained for various flow conditions with air flow rates ranging from 20 to 30 m³/h. For modelling, the flaming pyrolysis time for long-stick wood in the gasifier is calculated to be 1.6 min. The length of the flaming pyrolysis zone and char gasification zone is found to be 34 cm and 30 cm respectively. The rate of feed was between 9 and 10 kg/h. Continuous operation for 5 h was used for three runs to study the performance. In this study we measured the temperature and pressure in the different zones as a function of airflow. We measured the gas flow and efficiency of the gasifier in order to determine its commercial potential for process and power industries.