Updraft gasification of juniper wood biomass using CO2–O2 and Air (N2–O2)

Biomass gasification is being considered as one of the most promising technologies for converting low-quality solid biomass fuel into gaseous fuel. Redberry juniper (Juniperus pinchotii), one of the woody species that dominate uncultivated lands in the southern great plains, USA, may have a great potential for bioenergy utilization. In this study, the results of gasification of juniper are presented. Juniper wood chips were gasified in an adiabatic fixed bed updraft gasifier using air and the mixture gas of carbon dioxide and oxygen (CO₂:O₂) as gasification medium. The effect of gasification parameters such as moisture contents, gasification mediums, and gasification temperature on produced gas properties and the tar yield were investigated. It was observed that oxy fuel gasification (the reaction of woody fuels with carbon dioxide) of juniper resulted in the increase of production of carbon monoxide, especially at higher peak gasification temperatures. As a result, the CO₂ gasification resulted in producing higher heating value gas (6264 kJ/nm³ with dilution of CO₂ and 19,750 kJ/nm³ inert free) compared to air gasification. For air gasification, it was observed that the updraft gasification produced large amount of the tar in the product gas (more than 100 g/nm³) for the fuels with moisture content between 6% and 11%. Generally, the tar yield increased with the increase of equivalence ratio (er) and moisture content. However, when the fuel moisture content reached 23.5%, the tar yield reduced significantly due low gasification temperature which reduced the less tar cracking.     

Performance of oil palm kernel shell gasification using a medium-scale downdraft gasifier

This article focused on the performance of oil palm kernel shell (PKS) gasification using a medium-scale downdraft gasifier with a feedstock capacity of 500 kg at a temperature range of 399–700°C and at a feed rate of 177 kg/h. This article is important for evaluating the reliability of PKS gasification for commercial power generation activities from biomass. The process performance was evaluated based on the syngas calorific value (CV), syngas flow rate, and its cold gas efficiency (CGE). The syngas flow rates and CVs were measured using a gas flow meter and a gas analyzer in real time. The data obtained were then analyzed to evaluate the performance of the process. The results showed that the CGE of the process was moderately high (51%) at 681°C, with a high syngas CV (4.45–4.89 MJ/Nm³) which was ideal for gas engine applications. The PKS gasification performance increased when the reactor temperature increased. Projections were made for the CGE and the syngas CV for the PKS gasification with increased reactor temperatures and it was found that these values could be increased up to 80% and 5.2 MJ/Nm^3, respectively at a reactor temperature of 900°C. In addition, the estimated power that could be generated was about 600 kW_e at a maximum operation of 500 kg/h of feed rate. Based on the analysis, a medium-scale PKS gasification is observed to be a promising process for power generation from biomass due to the favorable performance of the process.     

Combined steam-dry reforming of toluene in syngas over CaNiRu/Al2O3 catalysts

Cracking, steam reforming, dry reforming, and combined steam and dry reforming of toluene in model syngas were performed using catalysts to simulate tar removal produced during biomass gasification. The catalysts were prepared by adding Ru, Ca, and Mn to Ni-based catalysts, and their properties were measured using BET, pulse CO chemisorption, XRD and TG. In steam and dry reforming of toluene, a high toluene conversion was observed with increasing Ca content in the catalyst and catalysts containing Ca showed a higher activity than those containing Mn. In combined steam-dry reforming with syngas, 1%CaNiRu/Al₂O₃ indicated a conversion of 93.9% at 800°C.     

Long-term coal gasification-based power with near-zero emissions. Part B: Zecomag and oxy-fuel IGCC cycles

In this second part of the work, two other long-term technologies for power generation from coal are investigated. The Zecomag plant has the same syngas production system of the Zecomix plant, described in the first part of this paper, but hydrogen-rich syngas is here burned with air in an open-cycle gas turbine. The aim is a simplification of the power island, more similar to a combined cycle; however, CO₂ capture falls from 100% to about 90% and NO_x emissions are present.An advanced oxy-fuel IGCC is the second plant investigated in this paper, presenting the same zero-emission potential of Zecomix. Syngas is produced in a high pressure, dry feed, oxygen blown gasifier and cleaned in a hot-gas-clean-up system. Clean syngas is then burned with oxygen and expanded in a turbine, using compressed recirculated CO₂ to moderate firing temperature and to cool turbine blades.The loss of net efficiency, with respect to Zecomix, is very limited (1–2 points) with both configurations. In order to better evaluate the performances obtained, a comparison with reference state-of-the art IGCCs and a long-term IGCC without CO₂ capture is also presented.     

Gasification of Inferior Coal with High Ash Content under CO2 and O2/H2O Atmospheres

The gasification reaction of Nantong inferior coal was investigated in a laboratory fixed-bed reactor under CO₂ and O₂/H₂O atmospheres. The effects of the bed temperature and inlet-gas concentration on the yields of CO, H₂, and CH₄ were studied. The effects of coal ash and particle size on the fixed-carbon conversion were also investigated, and kinetic analysis was conducted with a homogeneous model. The product-gas-heating value and fixed-carbon conversion increased when the temperature was increased from 950 °C to 1100 °C under CO₂ atmosphere. When the inlet-CO₂ concentration was increased from 50 to 100 vol.%, the low heating value of the product gas and carbon conversion ratio slightly increased. During the gasification of inferior coal under the O₂/H₂O atmosphere, the CO concentration increased rapidly with increasing temperature. The H₂ and CH₄ concentrations increased initially and then decreased. The maximum gas heating value of 7934 kJ/m³ was obtained under the O₂ concentration of 70 vol.% at a bed temperature of 1050 °C. The cold-gas efficiency increased with increasing temperature and became 40.6% and 86.4% at 1100 °C under the CO₂ and O₂/H₂O atmospheres, respectively. The gasification reaction of the Nantong inferior coal strongly depended on the content of inherent inorganic matter. The gasification rates for both the CO₂ and O₂/H₂O atmospheres were independent of the particle size. The activation energy for the CO₂ and O₂/H₂O gasification reactions were 137 and 81 kJ/mol, respectively. The gasification reactions of the Nantong coal, which was performed under two different atmospheres, were compared and the reaction activity of the gasification reaction under CO₂ atmosphere was found to be much lower than that under the O₂/H₂O atmosphere.     

CO2 capture from pre-combustion processes—Strategies for membrane gas separation

The application of membrane gas separation to CO₂ capture from a coal gasification process is one potential solution to reduce greenhouse gas emissions. This review considers the potential for either H₂- or CO₂-selective membranes in an integrated gasification combined cycle (IGCC) process. In particular, the advantages and disadvantages of metallic, porous inorganic and polymeric membranes are considered. This analysis is extended to consider membrane technology as an enhancement to the water-gas shift reaction, to drive the production of hydrogen above the thermodynamic limit. The review concludes with a brief overview of the economics of incorporating membrane gas separation into the IGCC process and gives an indication of the potential economic use of membrane gas separation technology in the IGCC process.     

Reduction of CaSO4 oxygen carrier with coal in chemical-looping combustion: Effects of temperature and gasification intermediate

Chemical-looping combustion (CLC) has been suggested as an energy efficient method for the capture of carbon dioxide from combustion. Thermodynamics and kinetics of CaSO₄ reduction with coal via gasification intermediate in a CLC process were discussed in the paper, with respect to the CO₂ generating efficiency, the environmental factor and the surface morphology of oxygen carrier. Tests on the combined process of coal gasification and CaSO₄ reduction with coal syngas were conducted in a batch fluidized bed reactor at different reaction temperatures and with different gasification intermediates. The products were characterized by gas chromatograph, gas analyzers and scanning electron microscope. And the results showed that an increase in the reaction temperature aggravated the SO₂ emission. The CO₂ generating efficiency also increased with the temperature, but it decreased when the temperature exceeded 950 °C due to the sintering of oxygen carrier particles. The use of CO₂ as gasification intermediate in the fuel reactor had a positive effect on the sintering-resistant of oxygen carrier particles. However, increasing the steam/CO₂ ratio in gasification intermediate evidently enhanced CO₂ generating efficiency and reduced SO₂ environmental impact.     

Processing of Straw/Corn Stover: Comparison of Life Cycle Emissions

The LCA emissions from four renewable energy routes that convert straw/corn stover into usable energy are examined. The conversion options studied are ethanol by fermentation, syndiesel by oxygen gasification followed by Fischer Tropsch synthesis, and electricity by either direct combustion or biomass integrated gasification and combined cycle (BIGCC). The greenhouse gas (GHG) emissions of these four options are evaluated, drawing on a range of studies, and compared to the conventional technology they would replace in a western North American setting. The net avoided GHG emissions for the four energy conversion processes calculated relative to a “business as usual” case are 830 g CO₂e/kWh for direct combustion, 839 g CO₂e/kWh for BIGCC, 2,060 g CO₂e/L for ethanol production, and 2,440 g CO₂e/L for FT synthesis of syndiesel. The largest impact on avoided emissions arises from substitution of biomass for fossil fuel. Relative to this, the impact of emissions from processing of fossil fuel, e.g., refining of oil to produce gasoline or diesel, and processing of biomass to produce electricity or transportation fuels, is minor.     

The use of petroleum coke as fuel in a 10 kWth chemical-looping combustor

Tests were made in a 10 kW_th chemical-looping combustor with a petroleum coke as the solid fuel and the oxygen carrier ilmenite, an iron titanium oxide. The fuel reactor is fluidized by steam and the oxygen carrier reacts with the volatiles released as well as the gasification intermediates CO and H₂. A constant fuel flow corresponding to a thermal power of 5.8 kW was introduced into the fuel reactor and a total of 11 h of operation was reached. The effects of particle circulation and carbon stripper operation on solid fuel conversion, conversion of gas from the fuel reactor and CO₂ capture were investigated. The actual CO₂ capture ranged between 60% and 75% while the solid fuel conversion was in the range of 66–78%. The low values of solid fuel conversion reflect loss of char due to low efficiency of the fuel reactor cyclone. The incomplete conversion of the gas from the fuel reactor is expressed as oxygen demand. The oxygen demand corresponds to the fraction of oxygen lacking to achieve full gas conversion and was typically 25%, due to presence of CH₄, CO and H₂ from the fuel reactor. Typical ratios of CH₄, CO and H₂ over the total gaseous carbon from the fuel reactor are respectively 5, 10 and 25%. Low loss of non-combustible fines from the system indicates very low attrition of the oxygen carrier.     

Heterostructure CdS/ZnS nanoparticles as a visible light-driven photocatalyst for hydrogen generation from water

(CdS)_x/(ZnS)_1–x nanoparticles were synthesized as a visible light-driven photocatalyst using the stepped microemulsion technique with a series of the ratio factors (x). The photocatalytic test results showed that (CdS)_x/(ZnS)_1-x with x = 0.8 had the highest photo-reactivity for H₂ production from water under visible light. The composite (CdS)_0.8/(ZnS)_0.2 catalyst had a heterogeneous structure that exhibited a much greater photocatalytic hydrogen production activity than either pure CdS or the homogeneous Cd_0.8Zn_0.2S solid solution. ZnS deposition also was shown to largely improve the stability of CdS in the heterostructured CdS/ZnS catalyst. Thermal treatment of the catalyst, i.e., annealing (CdS)_0.8/(ZnS)_0.2 at 723 K, improved the crystallinity of the catalyst and increased its photocatalytic H₂ production rate by more than 36 times. Deposition of Ru on the surface of the catalyst particles by in situ photo-deposition further increased the photo-H₂ generation rate by 3 times. The photocatalyst of 0.5%Ru/CdS/ZnS achieved the highest H₂ production activity, at a rate of 12650 μmol/g-h and with a light to hydrogen energy conversion efficiency of 6.5%.     

Validation of a dynamic model of hydrogen permeation through Pd-based membranes

Pd-based membranes have been studied for pure hydrogen separation from syngas: in particular, a mathematical model of a Pd membrane for hydrogen separation has been developed.This model can be used in process and assessment studies of the parameters which characterize the mass transfer phenomena (such as: hydrogen permeability, surface coverage and limiting step). By coupling the permeation and water gas shift reaction kinetics, it can also be used to evaluate the performances of the membrane reactor. Further, it can be helpful to evaluate the best assembly and sizing of a H₂/CO₂ separation system.The model takes into account the kinetics of H₂ adsorption/desorption on Pd surface, the H₂ permeation into the palladium bulk and in the porous layer, and the kinetics of CO, CO₂, H₂O, O₂, H₂S competitive adsorption/desorption on Pd surface. It is also comprehensive of flux equations and bulk mass, momentum and energy balance.The results released by the model were compared to the experimental data during both the transient phase and the steady state conditions. A satisfactory agreement between model and experimental data was found.     

TGA analysis of tobacco rob pyrolysis and release characteristics of noncondensable gas in a fixed-bed reactor

In this study, the size of tobacco rob (TR) particle was considered as a major factor in determining the mass loss in thermogravimetric analysis (TGA) and product yield and composition at different reactor temperatures in the fixed-bed reactor. The TGA results showed that the conversion rate increased and the activation energy (ranged from 53.29 to 58.25 kJ/mol) decreased with a decrease in particle size. The experiments demonstrated that fuel gas yield (from 0.76 to 0.82 Nm³/kg at 900 °C) increased with a decrease in particle size while char and tar yield decreased. Smaller particle sizes resulted in higher H₂ (25.68%) and CO (27.36%) contents. Minimizing the size of raw materials is an alternative method to improve the gas quality of TR pyrolysis. The increase of gas yield was attributed to the decomposition of char and tar vapor as temperature increased.     

Chemical-looping combustion using syngas as fuel

Chemical-looping combustion (CLC) is a combustion technology where an oxygen carrier is used to transfer oxygen from the combustion air to the fuel, avoiding direct contact between air and fuel. Thus, CO₂ and H₂O are inherently separated from the rest of the flue gases and the carbon dioxide can be obtained in a pure form without the use of an energy intensive air separation unit. The paper presents results from a 3-year project devoted to developing the CLC technology for use with syngas from coal gasification. The project has focused on: (i) the development of oxygen carrier particles, (ii) establishing a reactor design and feasible operating conditions and (iii) construction and operation of a continuously working hot reactor. Approximately, 300 different oxygen carriers based on oxides of the metals Ni, Fe, Mn and Cu were investigated with respect to parameters, which are important in a CLC system, and from these investigations, several particles were found to possess suitable qualities as oxygen carriers. Several cold-model prototypes of CLC based on interconnected fluidized bed reactors were tested, and from these tests a hot prototype CLC reactor system was constructed and operated successfully using three carriers based on Ni, Fe and Mn developed within the project. The particles were used for 30–70 h with combustion, but were circulated under hot conditions for 60–150 h.     

Long-term coal gasification-based power plants with near-zero emissions. Part A: Zecomix cycle

These two part papers analyse three plant configurations for high efficiency, near-zero emissions power generation from coal, suitable for long-term installations. In the first part the Zecomix cycle, a novel power plant based on various innovative processes, is presented. Zecomix plant is based on a coal hydrogasification process, using recycled steam and hydrogen as gasifying agents, to produce a CH₄ rich syngas. Methane is then converted to an H₂/H₂O based syngas and CO₂ is captured, by reacting in two carbonator reactors with CaO-based solid sorbent. CaCO₃ produced in carbonators is thermally regenerated in a calciner. The synthetic fuel is burned with oxygen in a semi-closed high temperature steam cycle, with a supercritical heat recovery.The paper presents a detailed analysis of the thermodynamic aspects of the process, with the scope of assessing its potential performance in terms of efficiency and emissions. Main operating parameters of the chemical island (e.g. hydrogasifier and calciner pressure, steam flow rates to carbonators, syngas recycle fraction) and of the power island (e.g. pressure ratio, turbine inlet temperature and reheat pressure) were varied in order to evaluate their effect on plant performance and to optimize the process. Critical issues are specifically discussed: the calcination process, the calcium oxide utilization in carbonators, the cooling requirement of the high temperature turbine, the presence of incondensable species in the steam cycle. An accurate performance estimation is therefore developed by considering advanced components, as an evolution of today's technology, excluding unproven devices whose feasibility cannot be anticipated.Depending on sorbent utilization, a net plant efficiency of 44–47% with a virtually complete carbon capture was obtained, a very interesting result with respect to other proposed coal-fired power plants with carbon capture. The high complexity of the chemical island and the importance of a good sorbent performance should be however taken into account for a fair comparison with other plant concepts. Further experimental investigations are mandatory to demonstrate the technical and economical feasibility of the Zecomix plant.     

Effect of oxygenated liquid additives on the urea based SNCR process

An experimental investigation was performed to study the effect of oxygenated liquid additives, H₂O₂, C₂H₅OH, C₂H₄(OH)₂ and C₃H₅(OH)₃ on NO_x removal from flue gases by the selective non-catalytic reduction (SNCR) process using urea as a reducing agent. Experiments were performed with a 150 kW pilot scale reactor in which a simulated flue gas was generated by the combustion of methane operating with 6% excess oxygen in flue gases. The desired levels of initial NO_x (500 ppm) were achieved by doping the fuel gas with ammonia. Experiments were performed throughout the temperature range of interest, i.e. from 800 to 1200 °C for the investigation of the effects of the process additives on the performance of aqueous urea DeNO_x. With H₂O₂ addition a downward shift of 150 °C in the peak reduction temperature from 1130 to 980 °C was observed during the experimentation, however, the peak reduction efficiency was reduced from 81 to 63% when no additive was used. The gradual addition of C₂H₅OH up to a molar ratio of 2.0 further impairs the peak NO_x reduction efficiency by reducing it to 50% but this is accompanied by a downward shift of 180 °C in the peak reduction temperature. Further exploration using C₂H₄(OH)₂ suggested that a 50% reduction could be attained for all the temperatures higher than 940 °C. The use of C₃H₅(OH)₃ as a secondary additive has a significant effect on the peak reduction efficiency that decreased to 40% the reductions were achievable at a much lower temperature of 800 °C showing a downward shift of 330 °C.     

Electricity systems with near-zero emissions of CO2 based on wind energy and coal gasification with CCS and hydrogen storage

Emissions from electricity generation will have to be reduced to near-zero to meet targets for reducing overall greenhouse gas emissions. Variable renewable energy sources such as wind will help to achieve this goal but they will have to be used in conjunction with other flexible power plants with low-CO₂ emissions. A process which would be well suited to this role would be coal gasification hydrogen production with CCS, underground buffer storage of hydrogen and independent gas turbine power generation. The gasification hydrogen production and CO₂ capture and storage equipment could operate at full load and only the power plants would need to operate flexibly and at low load, which would result in substantial practical and economic advantages. This paper analyses the performances and costs of such plants in scenarios with various amounts of wind generation, based on data for power demand and wind energy variability in the UK. In a scenario with 35% wind generation, overall emissions of CO₂ could be reduced by 98–99%. The cost of abating CO₂ emissions from the non-wind residual generation using the technique proposed in this paper would be less than 40% of the cost of using coal-fired power plants with integrated CCS.     

Operating experience with chemical looping combustion in a 120 kW dual circulating fluidized bed (DCFB) unit

This study presents first operating experience with a 120 kW chemical looping pilot rig. The dual circulating fluidized bed reactor system and its auxiliary units are discussed. Two different oxygen carriers, i.e. ilmenite, which is a natural iron titanium ore, and a designed Ni-based particle, are tested in the CLC unit. The pilot rig is fueled with H₂, CO and CH₄ respectively at a fuel power of 65–145 kW. High solids circulation, very low solids residence time and low solids inventory are observed during operation. Owing to the scalability of the design concept, these characteristics should be quite similar to those of commercial CLC power plants. Ilmenite shows a high potential for the combustion of H₂-rich gases (e.g. from coal gasification with steam). The H₂ conversion is quite high but there is still a high potential for further improvement. The Ni-based oxygen carrier achieves the thermodynamic maximum H₂ and CO conversion and also very high CH₄ conversion. A variation of the air/fuel ratio and the reaction temperature indicates that the Ni/NiO ratio of the particle has an influence on the performance of the chemical looping combustor. Generally, low solids conversion in air and fuel reactors is observed in almost any conditions. Despite a very low H₂O/CH₄ molar ratio, no carbon formation is observed.     

Relationship between liquid depth and the acoustic generation of hydrogen: design aspect for large cavitational reactors with special focus on the role of the wave attenuation

Understanding the effect of the liquid depth (z) on the acoustic generation of hydrogen is highly required for designing large-scale sonoreactors for hydrogen production because acoustic cavitation is the central event that initiates sonochemical reactions. In this paper, we present a computational analysis of the liquid-depth effect on the generation of H₂ from a reactive acoustic bubble trapped in water irradiated with an attenuating sinusoidal ultrasound wave. The computations were made for different operating conditions of frequency (355–1000 kHz), acoustic intensity (1–5 W/cm²), and liquid temperature (10–30°C). The contribution of the acoustic wave attenuation on the overall effect of depth was appreciated for the different conditions. It was found that the acoustic generation of hydrogen diminished hardly with increasing depth up to z = 8 m, and the depth effect was strongly operating parameter-dependent. The sound wave attenuation played a crucial role in quenching H₂ yield, particularly at higher z. The reduction of the H₂ yield with depth was more pronounced at higher frequency (1000 kHz) and lower temperature (10°C) and acoustic intensity (1 W/cm²). The attenuation of the sound wave may contribute up to 100% in the overall reductive effect of depth toward H₂ production rate. This parameter could be imperatively included when studying all aspects of underwater acoustic cavitation.     

Steam reforming of glycerol for syngas generation under cold plasma conditions: A DFT study

Density functional theory (DFT) has been used to investigate the reaction pathways with steam reforming of glycerol under cold plasma conditions. Total energies, energy barriers, and reaction enthalpies at 298.15 K have been calculated at the GGA/PW91/DNP level. The calculation shows that, with the presence of steam, the energy barrier of glycerol conversion is reduced and the conversion from glycerol to H₂ and CO is promoted under cold plasma conditions. The formation of syngas was through a multi-step pathway via the conversion of OHCH₂CHOH, CH₂OH, CH₂O, HCO,·and CH₃, while the recombination of H generated extra H₂. The synthesis of hydrocarbons are from the recombination of·CH₃,·CH₂, and·CH, which could be primarily generated through glycerol dissociation. The structure of glycerol anion was also studied in this work, and it was less stable than the neutral molecule. The route for the formation of OHCH₂CHOH·and CH₂OH·from glycerol anion is thermodynamically favorable.     

Demonstration of a high throughput on-board hydrogen generation reactor system using aluminum coil as fuel for a vehicle

A novel on-board hydrogen generation concept using Al coil with NaOH was investigated. The reaction rate was successfully controlled by introducing a pumping system for the NaOH solution. The time for the flow to develop fully was mainly dependent on the solution temperature, and the fastest start time recorded was 60 sec at a solution temperature of 70°C. The maximum H₂ generation rate was 200 L min^–1 with a prototype design of the on-board hydrogen generation system 1/8 times the size of a full-size reactor. The H₂ generation process coupled with the solution pumping system was simulated with three-dimensional fluid dynamic software, and the calculated H₂ flow and temperature rise of the system were validated with experimental data.