A CFD approach on the effect of particle size on char entrainment in bubbling fluidised bed reactors

The fluid – particle interaction inside a 41.7 mg s-1 fluidised bed reactor is modelled. Three char particles of sizes 500 µm, 250 µm, and 100 µm are injected into the fluidised bed and the momentum transport from the fluidising gas and fluidised sand is modelled. Due to the fluidising conditions and reactor design the char particles will either be entrained from the reactor or remain inside the bubbling bed. The particle size is the factor that differentiates the particle motion inside the reactor and their efficient entrainment out of it. A 3-Dimensional simulation has been performed with a completele revised momentum transport model for bubble three-phase flow according to the literature as an extension to the commercial finite volume code FLUENT 6.2.

HTHP syngas cleaning concept of two stage biomass gasification for FT synthesis

The EU intends to increase the fraction of fuels from biogenic energy sources from 2% in 2005 to 8% in 2020. This means a minimum of 30 million TOE/a of fuels from biomass. This makes technical-scale generation of syngas from high-grade biomass, e.g. straw, hay, bark, or paper/cardboard waste, and the production of synthetic fuels by Fischer-Tropsch (FT) synthesis highly attractive. The BTL concept (Biomass to Liquids) of the Karlsruhe Research Center, labeled bioliq, focuses on this challenge by locally concentrating the biomass energy content by fast pyrolysis in a coke/oil slurry followed by slurry conversion to syngas in a central entrained flow gasifier at 1200C and pressures above 4MPa. FT synthesis generates intermediate products for synthetic fuels. To prevent the sensitive catalysts from being poisoned the syngas must be free of tar and particulates. Trace concentrations of H2S, COS, CS2, HCl, NH3, and HCN must be on the order of a few ppb. Moreover, maximum conversion efficiency will be achieved by cleaning the gas above the synthesis conditions. (T>350C, P>4MPa). The concept of an innovative dry HTHP syngas cleaning process is presented. Based on HT particle filtration and suitable sorption and catalysis processes for the relevant contaminants, an overall concept will be derived, which leads to a syngas quality required for FT synthesis in only two combined stages. Results of filtration experiments on a pilot scale are presented. The influence of temperature on the separation and conversion, respectively, of particulates and gaseous contaminants is discussed on the basis of experimental results obtained on a laboratory and pilot scale. Extensive studies of this concept are performed in a scientific network comprising the Karlsruhe Research Center and five universities; funding is provided by the Helmholtz Association of National Research Centers in Germany.

A comparative study on the pyrolysis of metal- and ash-enriched wood and the combustion properties of the gained char

This study aims to investigate the pyrolysis behaviour of metal-contaminated wood and the combustion properties of char derived from wood pyrolysis. Seven metals (Na, Mg, Ca, Zn, Cd, Pb and Fe(III)) were introduced to willow in cation form by ion-exchange and the thermal behaviour of demineralised samples and samples with additional ash were also investigated. The results show that the char yield increased from 21% to 24-28% and levoglucosan yield in vapour phase decreased from 88% to 62-29% after the addition of inorganic compounds, even though the metal binding capacity of wood varied from one metal ion to another. While char yield seems to be effected mainly by the concentration of the metal ions, levoglucosan yield was more dependent on the ionic species especially when sodium ions were present. When combustion experiments were carried out with char made of the metal enriched wood, two consecutive steps were observed, both effected by the presence of inorganic compounds. The first step was identified as the release and combustion of volatiles, while the second peak of the burning profile is the actual combustion of the fixed carbon. The burnout temperatures, estimated ignition indices and the conversion indicate that the type and not the amount of metal ions were the determining factors during the second step of combustion. © 2012 Published by Elsevier B.V.

High temperature gas cleaning for advanced syngas utilization:Paper # 95

Biofuels and chemicals from biomass mean the gasification of biogenic feedstocks and the synthesis via methanol, dimethylester (DME) or Fischer-Tropsch products. To prevent the sensitive synthesis catalysts from poisoning the syngas must be free of tar and particulates. The trace concentrations of S-, C1-, N-species, alkali and heavy metals must be of the order of a few ppb. Moreover maximum conversion efficiency will be achieved performing the gas cleaning above the synthesis conditions. The concept of an innovative dry HTHP syngas cleaning is presented. Based on the HT particle filtration and suitable sorption and catalysis processes for the relevant contaminants a total concept will be derived, which leads to a syngas quality required for synthesis catalysts in only 2 combined stages. The experimental setup for the HT gas cleaning behind the 60 kWtherm entrained flow gasifier REGA of the institute is described. Results from HT filter experiments in pilot scale are presented. The performance of 2 natural minerals for HC1 and H2S sorption is discussed with respect to the parameters temperature, surface and residence time. Results from lab scale investigations on low temperature tar catalysts' performance (commercial and proprietary development) are discussed finally.

3D simulation of the effects of sphericity on char entrainment in fluidised beds

The paper presents a 3-dimensional simulation of the effect of particle shape on char entrainment in a bubbling fluidised bed reactor. Three char particles of 350 μm side length but of different shapes (cube, sphere, and tetrahedron) are injected into the fluidised bed and the momentum transport from the fluidising gas and fluidised sand is modelled. Due to the fluidising conditions, reactor design and particle shape the char particles will either be entrained from the reactor or remain inside the bubbling bed. The sphericity of the particles is the factor that differentiates the particle motion inside the reactor and their efficient entrainment out of it. The simulation has been performed with a completely revised momentum transport model for bubble three-phase flow, taking into account the sphericity factors, and has been applied as an extension to the commercial finite volume code FLUENT 6.3. © 2010 Elsevier B.V.All rights reserved.

Encapsulation of phase change materials using rice-husk-char

This paper explored a new approach to prepare phase change microcapsules using carbon-based particles via Pickering emulsions for energy storage applications. Rice-husk-char, a by-product in biofuel production, containing 53.58 wt% of carbon was used as a model carbon-based material to encapsulate hexadecane. As a model phase change material, hexadecane was emulsified in aqueous suspensions of rice-husk-char nanoparticles. Water soluble polymers poly(diallyldimethyl-ammonium chloride) and poly(sodium styrene sulfonate) were used to fix the rice-husk-char nanoparticles on the emulsion droplets through layer-by-layer assembly to enhance the structural stability of the microcapsules. The microcapsules formed are composed of a thin shell encompassing a large core consisting of hexadecane. Thermal gravimetrical and differential scanning calorimeter analyses showed the phase change enthalpy of 80.9 kJ kg−1 or 120.0 MJ m−3. Design criteria of phase change microcapsules and preparation considerations were discussed in terms of desired applications. This work demonstrated possible utilisations of biomass-originated carbon-based material for thermal energy recovery and storage applications, which can be a new route of carbon capture and utilisation.

Pyrolysis of rice husk and corn stalk in auger reactor:Part 1. Characterization of char and gas at various temperatures

In this study, rice husk and corn stalk have been pyrolyzed in an auger pyrolysis reactor at pyrolysis temperatures of 350, 400, 450, 500, 550, and 600 °C in order to investigate the effect of the pyrolysis temperature on the pyrolysis performance of the reactor and physicochemical properties of pyrolysis products (this paper focuses on char and gas). The results have shown that the pyrolysis temperature significantly affects the mass yields and properties of the pyrolysis products. The mass yields of pyrolysis liquid and char are comparable to those reported for the same feedstocks processed in fluidized bed reactors. With the increase of the pyrolysis temperature, the pyrolysis liquid yield shows a peak at 500 °C, the char yield decreases, and the gas yield increases for both feedstocks. The higher heating value (HHV) and volatile matter content of char increase as the pyrolysis temperature increases from 350 to 600 °C. The gases obtained from the pyrolysis of rice husk and corn stalk mainly contain CO2, CO, CH4, H2, and other light hydrocarbons; the molar fractions of combustible gases increase and therefore their HHVs subsequently increase with the increase of the pyrolysis temperature.

Fuels from tyres by pyrolysis in molten salts

The current annual arisings of used car/van tyres in the U.K. has been found to be around 25m (188,000 tonnes). After the established reuse industries have taken their requirements this leaves 13.5m (102,000 tonnes) waste tyres; a quantity that can no longer be satisfactorily tipped. Laboratory scale experiments have shown that tyre can be pyrolised, using a molten carbonate system as the reaction medium, at rates corresponding to 14.9-42.7 g tyre/min. per litre of melt over the range 475 and 650°C. The product yields by weight of tyre input between the same temperatures are: hydrocarbon oil 23-36 wt. %, hydrocarbon gas 7- 18 wt. %, carbonaceous char 35-40 wt. %, steel 16.7 wt. % and inorganics 5.4 wt. %. The oil and gas evolve from the reactor and can easily be collected by conventional means. The steel and inorganics remain in the reactor although on the commercial scale it is proposed that they would be removed by physical and chemical methods respectively. The char was found to pose considerable handling problems and so a method was devised by which it could be gasified in the reactor. This was best achieved by passing air at a less than stoichiometric rate which gave a gaseous product rich in carbon monoxide. In addition this action provides heat for the system as a whole. The rates at 675-9000C were in the range corresponding to 5.6- 14.89 char/min. per litre of melt. A process flow chart has been proposed for a continuous operation based on these systems. Data from theoretical and experimental studies has enabled economic evaluations of several commercial scales to be carried out. These have shown that 4,000 and 10,000 t/yr operations show a DCF rate of return around 30% while a 50,000 t/yr operation shows 60% which would be attractive to an experienced scrap operator.

Thermochemical characterisation of straws and high yielding perennial grasses

The research is concerned with thermochemical characterisation of straws and high yielding perennial grasses. Crops selected for this study include wheat straw (Triticum aestivum), rape straw (Brassica napus), reed canary grass (Phalaris arundinacea) and switch grass (Panicum virgatum). Thermogravimetric analysis (TGA) was used to examine the distribution of char and volatiles during pyrolysis up to 900 °C. Utilising multi-heating rate thermogravimetric data, the Friedman iso-conversional kinetic method was used to determine pyrolysis kinetic parameters. Light and medium volatile decomposition products were investigated using pyrolysis–gas chromatography–mass spectrometry (Py–GC–MS) up to 520 °C. The 22 highest yielding identifiable cellulose, hemicellulose and lignin biomass markers were semi-quantified taking into consideration peak areas from GC chromatograms. Notable differences can be seen in butanedioic acid, dimethyl ester (hemicelluloses decomposition products), 2-methoxy-4-vinylphenol (lignin marker) and levoglucosan (intermediate pyrolytic decomposition product of cellulose) content when comparing perennial grasses with straw. From results presented in this study, perennial grasses such as switch grass, have the most attractive properties for fast pyrolysis processing. This is because of the observed high volatile yield content of 82.23%, heating value of 19.64 MJ/kg and the relatively low inorganic content.

The effect of lignin and inorganic species in biomass on pyrolysis oil yields, quality and stability

This paper investigates four reference fuels and three low lignin Lolium Festuca grasses which were subjected to pyrolysis to produce pyrolysis oils. The oils were analysed to determine their quality and stability, enabling the identification of feedstock traits which affect oil stability. Two washed feedstocks were also subjected to pyrolysis to investigate whether washing can enhance pyrolysis oil quality. It was found that the mineral matter had the dominate effect on pyrolysis in compared to lignin content, in terms of pyrolysis yields for organics, char and gases. However the higher molecular weight compounds present in the pyrolysis oil are due to the lignin derived compounds as determined by results of GPC and liquid-GC/MS. The light organic fraction also increased in yield, but reduced in water content as metals increased at the expense of the lignin content. It was found that the fresh oil and aged oil had different compound intensities/concentrations, which is due to a large number of reactions occurring when the oil is aged day by day. These findings agree with previous reports which suggest that a large amount of re-polymerisation occurs as levoglucosan yields increase during the aging progress, while hydroxyacetaldehyde decrease. In summary the paper reports a window for producing a more stable pyrolysis oil by the use of energy crops, and also show that washing of biomass can improve oil quality and stability for high ash feedstocks, but less so for the energy crops.

Application of CFD to model fast pyrolysis of biomass

The article deals with the CFD modelling of fast pyrolysis of biomass in an Entrained Flow Reactor (EFR). The Lagrangian approach is adopted for the particle tracking, while the flow of the inert gas is treated with the standard Eulerian method for gases. The model includes the thermal degradation of biomass to char with simultaneous evolution of gases and tars from a discrete biomass particle. The chemical reactions are represented using a two-stage, semi-global model. The radial distribution of the pyrolysis products is predicted as well as their effect on the particle properties. The convective heat transfer to the surface of the particle is computed using the Ranz-Marshall correlation.

CFD modelling of the fast pyrolysis of an in-flight cellulosic particle subjected to convective heat transfer

The pyrolysis of a freely moving cellulosic particle inside a 41.7mgs -1 source continuously fed fluid bed reactor subjected to convective heat transfer is modelled. The Lagrangian approach is adopted for the particle tracking inside the reactor, while the flow of the inert gas is treated with the standard Eulerian method for gases. The model incorporates the thermal degradation of cellulose to char with simultaneous evolution of gases and vapours from discrete cellulosic particles. The reaction kinetics is represented according to the Broido–Shafizadeh scheme. The convective heat transfer to the surface of the particle is solved by two means, namely the Ranz–Marshall correlation and the limit case of infinitely fast external heat transfer rates. The results from both approaches are compared and discussed. The effect of the different heat transfer rates on the discrete phase trajectory is also considered.

Nitrogen cycle of effluent-irrigated energy crop plantations:from wastewater treatment to thermo-chemical conversion processes

This paper reviews nitrogen (N) cycle of effluent-irrigated energy crop plantations, starting from wastewater treatment to thermo-chemical conversion processes. In wastewater, N compounds contribute to eutrophication and toxicity in water cycle. Removal of N via vegetative filters and specifically in short-rotation energy plantations, is a relatively new approach to managing nitrogenous effluents. Though combustion of energy crops is in principle carbon neutral, in practice, N content may contribute to NOx emissions with significant global warming potential. Intermediate pyrolysis produces advanced fuels while reducing such emissions. By operating at intermediate temperature (500°C), it retains most N in char as pyrrolic-N, pyridinic-N, quaternary-N and amines. In addition, biochar provides long-term sequestration of carbon in soils.

Evaluation of catalytic pyrolysis of cassava rhizome by principal component analysis

Rhizome of cassava plants (Manihot esculenta Crantz) was catalytically pyrolysed at 500 °C using analytical pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS) method in order to investigate the relative effect of various catalysts on pyrolysis products. Selected catalysts expected to affect bio-oil properties were used in this study. These include zeolites and related materials (ZSM-5, Al-MCM-41 and Al-MSU-F type), metal oxides (zinc oxide, zirconium (IV) oxide, cerium (IV) oxide and copper chromite) catalysts, proprietary commercial catalysts (Criterion-534 and alumina-stabilised ceria-MI-575) and natural catalysts (slate, char and ashes derived from char and biomass). The pyrolysis product distributions were monitored using models in principal components analysis (PCA) technique. The results showed that the zeolites, proprietary commercial catalysts, copper chromite and biomass-derived ash were selective to the reduction of most oxygenated lignin derivatives. The use of ZSM-5, Criterion-534 and Al-MSU-F catalysts enhanced the formation of aromatic hydrocarbons and phenols. No single catalyst was found to selectively reduce all carbonyl products. Instead, most of the carbonyl compounds containing hydroxyl group were reduced by zeolite and related materials, proprietary catalysts and copper chromite. The PCA model for carboxylic acids showed that zeolite ZSM-5 and Al-MSU-F tend to produce significant amounts of acetic and formic acids.

Numerical Comparison of the Drag Models of Granular Flows Applied to the Fast Pyrolysis of Biomass

The paper presents a comparison between the different drag models for granular flows developed in the literature and the effect of each one of them on the fast pyrolysis of wood. The process takes place on an 100 g/h lab scale bubbling fluidized bed reactor located at Aston University. FLUENT 6.3 is used as the modeling framework of the fluidized bed hydrodynamics, while the fast pyrolysis of the discrete wood particles is incorporated as an external user defined function (UDF) hooked to FLUENT’s main code structure. Three different drag models for granular flows are compared, namely the Gidaspow, Syamlal O’Brien, and Wen-Yu, already incorporated in FLUENT’s main code, and their impact on particle trajectory, heat transfer, degradation rate, product yields, and char residence time is quantified. The Eulerian approach is used to model the bubbling behavior of the sand, which is treated as a continuum. Biomass reaction kinetics is modeled according to the literature using a two-stage, semiglobal model that takes into account secondary reactions.