Thermochemical conversion of Brewers Spent Grain combined with catalytic reforming of pyrolysis vapours

The brewing process is an energy intensive process that uses large quantities of heat and electricity. To produce this energy requires a high, mainly fossil fuel consumption and the cost of this is increasing each year due to rising fuel costs. One of the main by-products from the brewing process is Brewers Spent Grain (BSG), an organic residue with very high moisture content. It is widely available each year and is often given away as cattle feed or disposed of to landfill as waste. Currently these methods of disposal are also costly to the brewing process. The focus of this work was to investigate the energy potential of BSG via pyrolysis, gasification and catalytic steam reforming, in order to produce a tar-free useable fuel gas that can be combusted in a CHP plant to develop heat and electricity. The heat and electricity can either be used on site or exported. The first stage of this work was the drying and pre-treatment of BSG followed by characterisation to determine its basic composition and structure so it can be evaluated for its usefulness as a fuel. A thorough analysis of the characterisation results helps to better understand the thermal behaviour of BSG feedstock so it can be evaluated as a fuel when subjected to thermal conversion processes either by pyrolysis or gasification. The second stage was thermochemical conversion of the feedstock. Gasification of BSG was explored in a fixed bed downdraft gasifier unit. The study investigated whether BSG can be successfully converted by fixed bed downdraft gasification operation and whether it can produce a product gas that can potentially run an engine for heat and power. In addition the pyrolysis of BSG was explored using a novel “Pyroformer” intermediate pyrolysis reactor to investigate the behaviour of BSG under these processing conditions. The physicochemical properties and compositions of the pyrolysis fractions obtained (bio-oil, char and permanent gases) were investigated for their applicability in a combined heat power (CHP) application.

Sylow P-Subgroups of Abelian Group Rings

2000 Mathematics Subject Classification: Primary 20C07, 20K10, 20K20, 20K21; Secondary 16U60, 16S34.

q-Leibniz Algebras

2000 Mathematics Subject Classification: Primary 17A32, Secondary 17D25.

Biomass fast pyrolysis energy balance of a 1kg/h test rig

The present paper offers a methodological approach towards the estimation and definition of enthalpies constituting an energy balance around a fast pyrolysis experiment conducted in a laboratory scale fluid bed with a capacity of 1 kg/ h. Pure N2 was used as fluidization medium at atmospheric pressure and the operating temperature (∼500°C) was adjusted with electrical resistors. The biomass feedstock type that was used was beech wood. An effort was made to achieve a satisfying 92.5% retrieval of products (dry basis mass balance) with the differences mainly attributed to loss of some bio-oil constituents into the quenching medium, ISOPAR™. The chemical enthalpy recovery for bio-oil, char and permanent gases is calculated 64.6%, 14.5% and 7.1%, respectively. All the energy losses from the experimental unit into the environment, namely the pyrolyser, cooling unit etc. are discussed and compared to the heat of fast pyrolysis that was calculated at 1123.5 kJ per kg of beech wood. This only represents 2.4% of the biomass total enthalpy or 6.5% its HHV basis. For the estimation of some important thermo-physical properties such as heat capacity and density, it was found that using data based on the identified compounds from the GC/MS analysis is very close to the reference values despite the small fraction of the bio-oil components detected. The methodology and results can help as a starting point for the proper design of fast pyrolysis experiments, pilot and/or industrial scale plants.

The thermal performance of the polysaccharides extracted from hardwood:cellulose and hemicellulose

The pyrolytic behaviour of individual component in biomass needs to be understood to gain insight into the mechanism of biomass pyrolysis. A comparative study on the pyrolysis of cellulose (hexose-based polysaccharides) and hemicallulose (pentose-based polysaccharides) is performed by two sets of experiments including TG analysis and Py-GC-MS/FTIR. The samples of these two polysaccharide components are thermally decomposed in TGA at the heating rate of 5 and 60 K/min to demonstrate the different characteristics of mass loss stage(s) between them. The yield of pyrolytic products is examined by a fluidized-bed fast pyrolysis unit. The experiment confirms that cellulose mainly contributes to bio-oil production (reaching the maximum of 72% at 580 °C), while hemicellulose works as an important precursor for the char production (∼25%). The compounds in the gaseous mixture (CO and CO2) and bio-oil (levoglucosan, furfural, aldehyde, acetone and acetic acid) are further characterized by GC-MS for cellulose and GC-FTIR for hemicellulose, and their formations are investigated thoroughly. © 2010 Elsevier Ltd. All rights reserved.

Experimental validation of a predictive pyrolysis model in AspenPlus®

A novel simulation model for pyrolysis processes oflignocellulosicbiomassin AspenPlus (R) was presented at the BC&E 2013. Based on kinetic reaction mechanisms, the simulation calculates product compositions and yields depending on reactor conditions (temperature, residence time, flue gas flow rate) and feedstock composition (biochemical composition, atomic composition, ash and alkali metal content). The simulation model was found to show good correlation with existing publications. In order to further verify the model, own pyrolysis experiments in a 1 kg/h continuously fed fluidized bed fast pyrolysis reactor are performed. Two types of biomass with different characteristics are processed in order to evaluate the influence of the feedstock composition on the yields of the pyrolysis products and their composition. One wood and one straw-like feedstock are used due to their different characteristics. Furthermore, the temperature response of yields and product compositions is evaluated by varying the reactor temperature between 450 and 550 degrees C for one of the feedstocks. The yields of the pyrolysis products (gas, oil, char) are determined and their detailed composition is analysed. The experimental runs are reproduced with the corresponding reactor conditions in the AspenPlus model and the results compared with the experimental findings.

Energy conversion assessment of vacuum, slow and fast pyrolysis processes for low and high ash paper waste sludge

The performance of vacuum, slow and fast pyrolysis processes to transfer energy from the paper waste sludge (PWS) to liquid and solid products was compared. Paper waste sludges with low and high ash content (8.5 and 46.7 wt.%) were converted under optimised conditions for temperature and pellet size to maximise both product yields and energy content. Comparison of the gross energy conversions, as a combination of the bio-oil/tarry phase and char (ECsum), revealed that the fast pyrolysis performance was between 18.5% and 20.1% higher for the low ash PWS, and 18.4% and 36.5% higher for high ash PWS, when compared to the slow and vacuum pyrolysis processes respectively. For both PWSs, this finding was mainly attributed to higher production of condensable organic compounds and lower water yields during FP. The low ash PWS chars, fast pyrolysis bio-oils and vacuum pyrolysis tarry phase products had high calorific values (∼18-23 MJ kg-1) making them promising for energy applications. Considering the low calorific values of the chars from alternative pyrolysis processes (∼4-7 MJ kg-1), the high ash PWS should rather be converted to fast pyrolysis bio-oil to maximise the recovery of usable energy products.

Expanding the biomass resource:sustainable oil production via fast pyrolysis of low input high diversity biomass and the potential integration of thermochemical and biological conversion routes

Waste biomass is generated during the conservation management of semi-natural habitats, and represents an unused resource and potential bioenergy feedstock that does not compete with food production. Thermogravimetric analysis was used to characterise a representative range of biomass generated during conservation management in Wales. Of the biomass types assessed, those dominated by rush (Juncus effuses) and bracken (Pteridium aquilinum) exhibited the highest and lowest volatile compositions respectively and were selected for bench scale conversion via fast pyrolysis. Each biomass type was ensiled and a sub-sample of silage was washed and pressed. Demineralization of conservation biomass through washing and pressing was associated with higher oil yields following fast pyrolysis. The oil yields were within the published range established for the dedicated energy crops miscanthus and willow. In order to examine the potential a multiple output energy system was developed with gross power production estimates following valorisation of the press fluid, char and oil. If used in multi fuel industrial burners the char and oil alone would displace 3.9 × 105 tonnes per year of No. 2 light oil using Welsh biomass from conservation management. Bioenergy and product development using these feedstocks could simultaneously support biodiversity management and displace fossil fuels, thereby reducing GHG emissions. Gross power generation predictions show good potential.

A hydrothermally stable transition alumina by condensation-enhanced self-assembly and pyrolysis crystallization:application in the steam reforming of methane

The preparation of a steam-based hydrothermally stable transition alumina is reported. The gel was derived from a synthetic sol-gel route where Al-tri-sec-butoxide is hydrolysed in the presence of a non-ionic surfactant (EO20PO70EO20), HCl as the catalyst and water (H2O/Al = 6); the condensation was enhanced by treating the hydrolysed gel with tetrabutylammonium hydroxide (TBAOH), after which it was dried at 60 °C by solvent evaporation. The so-obtained mesophase was crystallized under argon at 1200 °C (1 h) producing a transition alumina containing δ/α, and possibly θ, alumina phases. Due to its surface acidity, the pyrolysis conditions transform the block copolymer into a cross-linked char structure that embeds the alumina crystallites. Calcination at 650 °C generates a fully porous material by burning the char; a residual carbon of 0.2 wt.% was found, attributed to the formation of surface (oxy)carbides. As a result, this route produces a transition alumina formed by nanoparticles of about 30 nm in size on average, having surface areas in the range of 59-76 m2 g-1 with well-defined mesopores centered at 14 nm. The material withstands steam at 900 °C with a relative surface area rate loss lower than those reported for δ-aluminas, the state-of-the-art MSU-X γ-alumina and other pure γ-aluminas. The hydrothermal stability was confirmed under relevant CH4 steam reforming conditions after adding Ni; a much lower surface area decay and higher CH4 conversion compared to a state-of-the-art MSU-X based Ni catalyst were observed. Two effects are important in explaining the properties of such an alumina: the char protects the particles against sintering, however, the dominant effect is provided by the TBAOH treatment that makes the mesophase more resistant to coarsening and sintering. This journal is © the Partner Organisations 2014.

Pyrolysis of Napier grass in a fixed bed reactor:effect of operating conditions on product yields and characteristic

This study presents a report on pyrolysis of Napier grass stem in a fixed bed reactor. The effects of nitrogen flow (20 to 60 mL/min), and reaction temperature (450 to 650 degrees C) were investigated. Increasing the nitrogen flow from 20 to 30 mL/min increased the bio-oil yield and decreased both bio-char and non-condensable gas. 30 mL/min nitrogen flow resulted in optimum bio-oil yield and was used in the subsequent experiments. Reaction temperatures between 450 and 600 degrees C increased the bio-oil yield, with maximum yield of 32.26 wt% at 600 degrees C and a decrease in the corresponding bio-char and non-condensable gas. At 650 degrees C, reductions in the bio-oil and bio-char yields were recorded while the non-condensable gas increased. Water content of the bio-oil decreased with increasing reaction temperature, while density and viscosity increased. The observed pH and higher heating values were between 2.43 to 2.97, and 25.25 to 28.88 MJ/kg, respectively. GC-MS analysis revealed that the oil was made up of highly oxygenated compounds and requires upgrading. The bio-char and non-condensable gas were characterized, and the effect of reaction temperature on the properties was evaluated. Napier grass represents a good source of renewable energy when all pyrolysis products are efficiently utilized.

Tree Mortality following Prescribed Fire and a Storm Surge Event in Slash Pine (Pinus elliottii var. densa) Forests in the Florida Keys, USA

In fire-dependent forests, managers are interested in predicting the consequences of prescribed burning on postfire tree mortality. We examined the effects of prescribed fire on tree mortality in Florida Keys pine forests, using a factorial design with understory type, season, and year of burn as factors. We also used logistic regression to model the effects of burn season, fire severity, and tree dimensions on individual tree mortality. Despite limited statistical power due to problems in carrying out the full suite of planned experimental burns, associations with tree and fire variables were observed. Post-fire pine tree mortality was negatively correlated with tree size and positively correlated with char height and percent crown scorch. Unlike post-fire mortality, tree mortality associated with storm surge from Hurricane Wilma was greater in the large size classes. Due to their influence on population structure and fuel dynamics, the size-selective mortality patterns following fire and storm surge have practical importance for using fire as a management tool in Florida Keys pinelands in the future, particularly when the threats to their continued existence from tropical storms and sea level rise are expected to increase.

Avaliação do desempenho da paligorsquita modificada e do carvão da pirólise do lodo de esgoto no processo de degradação fotocatalítica do fenol

The uncontrolled disposal of wastewaters containing phenolic compounds by the industry has caused irreversible damage to the environment. Because of this, it is now mandatory to develop new methods to treat these effluents before they are disposed of. One of the most promising and low cost approaches is the degradation of phenolic compounds via photocatalysis. This work, in particular, has as the main goal, the customization of a bench scale photoreactor and the preparation of catalysts via utilization of char originated from the fast pyrolysis of sewage sludge. The experiments were carried out at constant temperature (50°C) under oxygen (410, 515, 650 and 750 ml min-1). The reaction took place in the liquid phase (3.4 liters), where the catalyst concentration was 1g L-1 and the initial concentration of phenol was 500 mg L-1 and the reaction time was set to 3 hours. A 400 W lamp was adapted to the reactor. The flow of oxygen was optimized to 650 ml min-1. The pH of the liquid and the nature of the catalyst (acidified and calcined palygorskite, palygorskite impregnated with 3.8% Fe and the pyrolysis char) were investigated. The catalytic materials were characterized by XRD, XRF, and BET. In the process of photocatalytic degradation of phenol, the results showed that the pH has a significant influence on the phenol conversion, with best results for pH equal to 5.5. The phenol conversion ranged from 51.78% for the char sewage sludge to 58.02% (for palygorskite acidified calcined). Liquid samples analyzed by liquid chromatography and the following compounds were identified: hydroquinone, catechol and maleic acid. A mechanism of the reaction was proposed, whereas the phenol is transformed into the homogeneous phase and the others react on the catalyst surface. For the latter, the Langmuir-Hinshelwood model was applied, whose mass balances led to a system of differential equations and these were solved using numerical methods in order to get estimates for the kinetic and adsorption parameters. The model was adjusted satisfactorily to the experimental results. From the proposed mechanism and the operating conditions used in this study, the most favored step, regardless of the catalyst, was the acid group (originated from quinone compounds), being transformed into CO2 and water, whose rate constant k4 presented value of 0.578 mol L-1 min-1 for acidified calcined palygorskite, 0.472 mol L-1 min-1 for Fe2O3/palygorskite and 1.276 mol L-1 min-1 for the sludge to char, the latter being the best catalyst for mineralization of acid to CO2 and water. The quinones were adsorbed to the acidic sites of the calcined palygorskite and Fe2O3/palygorskite whose adsorption constants were similar (~ 4.45 L mol-1) and higher than that of the sewage sludge char (3.77 L mol-1).

Avaliação do desempenho da paligorsquita modificada e do carvão da pirólise do lodo de esgoto no processo de degradação fotocatalítica do fenol

The uncontrolled disposal of wastewaters containing phenolic compounds by the industry has caused irreversible damage to the environment. Because of this, it is now mandatory to develop new methods to treat these effluents before they are disposed of. One of the most promising and low cost approaches is the degradation of phenolic compounds via photocatalysis. This work, in particular, has as the main goal, the customization of a bench scale photoreactor and the preparation of catalysts via utilization of char originated from the fast pyrolysis of sewage sludge. The experiments were carried out at constant temperature (50°C) under oxygen (410, 515, 650 and 750 ml min-1). The reaction took place in the liquid phase (3.4 liters), where the catalyst concentration was 1g L-1 and the initial concentration of phenol was 500 mg L-1 and the reaction time was set to 3 hours. A 400 W lamp was adapted to the reactor. The flow of oxygen was optimized to 650 ml min-1. The pH of the liquid and the nature of the catalyst (acidified and calcined palygorskite, palygorskite impregnated with 3.8% Fe and the pyrolysis char) were investigated. The catalytic materials were characterized by XRD, XRF, and BET. In the process of photocatalytic degradation of phenol, the results showed that the pH has a significant influence on the phenol conversion, with best results for pH equal to 5.5. The phenol conversion ranged from 51.78% for the char sewage sludge to 58.02% (for palygorskite acidified calcined). Liquid samples analyzed by liquid chromatography and the following compounds were identified: hydroquinone, catechol and maleic acid. A mechanism of the reaction was proposed, whereas the phenol is transformed into the homogeneous phase and the others react on the catalyst surface. For the latter, the Langmuir-Hinshelwood model was applied, whose mass balances led to a system of differential equations and these were solved using numerical methods in order to get estimates for the kinetic and adsorption parameters. The model was adjusted satisfactorily to the experimental results. From the proposed mechanism and the operating conditions used in this study, the most favored step, regardless of the catalyst, was the acid group (originated from quinone compounds), being transformed into CO2 and water, whose rate constant k4 presented value of 0.578 mol L-1 min-1 for acidified calcined palygorskite, 0.472 mol L-1 min-1 for Fe2O3/palygorskite and 1.276 mol L-1 min-1 for the sludge to char, the latter being the best catalyst for mineralization of acid to CO2 and water. The quinones were adsorbed to the acidic sites of the calcined palygorskite and Fe2O3/palygorskite whose adsorption constants were similar (~ 4.45 L mol-1) and higher than that of the sewage sludge char (3.77 L mol-1).

Characterization of wood biochar and evaluation of its adsorption potential for removal of sulphate from produced water in offshore oil and gas industry

This thesis analyses the potential of wood biochar as an adsorbent in removal of sulphate from produced water. In worldwide offshore oil and gas industry, a large volume of waste water is generated as produced water. Sulphur compounds present in these produced water streams can cause environmental problems, regulatory problems and operational issues. Among the various sulphur removal technologies, the adsorption technique is considered as a suitable method since the design is simple, compact, economical and robust. Biochar has been studied as an adsorbent for removal of contaminants from water in a number of studies due to its low cost, potential availability, and adsorptive characteristics. In this study, biochar produced through fast pyrolysis of bark, hardwood sawdust, and softwood sawdust were characterized through a series of tests and were analysed for adsorbent properties. Treating produced water using biochar sourced from wood waste is a two-fold solution to environmental problems as it reduces the volume of these wastes. Batch adsorption tests were carried out to obtain adsorption capacities of each biochar sample using sodium sulphate solutions. The highest sulphur adsorption capacities obtained for hardwood char, softwood char and bark char were 11.81 mg/g, 9.44 mg/g, and 7.94 mg/g respectively at 10 °C and pH=4. The adsorption process followed the second order kinetic model and the Freundlich isotherm model. Adsorption reaction was thermodynamically favourable and exothermic. The overall analysis concludes that the wood biochar is a feasible, economical, and environmental adsorbent for removal of sulphate from produced water.

Eating habits of a population undergoing a rapid dietary transition: portion sizes of traditional and non-traditional foods and beverages consumed by Inuit adults in Nunavut, Canada

Background: To determine the portion sizes of traditional and non-traditional foods being consumed by Inuit adults in three remote communities in Nunavut, Canada. Methods. A cross-sectional study was carried out between June and October, 2008. Trained field workers collected dietary data using a culturally appropriate, validated quantitative food frequency questionnaire (QFFQ) developed specifically for the study population. Results: Caribou, muktuk (whale blubber and skin) and Arctic char (salmon family), were the most commonly consumed traditional foods; mean portion sizes for traditional foods ranged from 10 g for fermented seal fat to 424 g for fried caribou. Fried bannock and white bread were consumed by >85% of participants; mean portion sizes for these foods were 189 g and 70 g, respectively. Sugar-sweetened beverages and energy-dense, nutrient-poor foods were also widely consumed. Mean portion sizes for regular pop and sweetened juices with added sugar were 663 g and 572 g, respectively. Mean portion sizes for potato chips, pilot biscuits, cakes, chocolate and cookies were 59 g, 59 g, 106 g, 59 g, and 46 g, respectively. Conclusions: The present study provides further evidence of the nutrition transition that is occurring among Inuit in the Canadian Arctic. It also highlights a number of foods and beverages that could be targeted in future nutritional intervention programs aimed at obesity and diet-related chronic disease prevention in these and other Inuit communities.