Hydrogen production by biomass gasification in a fluidized-bed reactor promoted by an Fe/CaO catalyst

Biomass gasification for hydrogen production was performed in a continuous-feeding fluidized-bed with the use of Fe/CaO catalysts. The relationship between catalyst properties and biomass gasification efficiencies was studied. The findings indicated that only CaO was involved in the enhancement of char gasification, resulting in an increased hydrogen production. However, CaO was also easily deactivated by biomass tar. The characterization results indicated that when CaO was impregnated with Fe, Ca₂Fe₂O₅ formed on the surface of the support. Ca₂Fe₂O₅ decomposed polyaromatic tar but was not effective in char gasification. The synergistic effects between Fe and CaO that effectively enhanced biomass gasification mainly involved combustion and pyrolysis, and the biomass gasification products, i.e., char and tar, were further gasified, indicating that tailor-made Fe/CaO catalysts prevented CaO deactivation by tar, thus promoting biomass gasification and hydrogen production.     

Exergy analysis of biomass staged-gasification for hydrogen-rich syngas

Using Aspen Plus simulations, exergy analyses of hydrogen-rich syngas production via biomass staged-gasification are carried out for three configurations, namely, staged-gasification with pyrolysis gas combustion and char gasification (C-1), staged-gasification with pyrolysis gas reforming and char gasification (C-2), and staged-gasification with pyrolysis gas reforming and char combustion (C-3). The results show that, for the gasification and reforming processes, the exergy loss of pyrolysis gas with tar reforming is less than that of char gasification. As for the system, it is conducive to generating hydrogen by making full use of the hydrogen element (H) in biomass instead of the H in water. The benefits of C-1 are that it removes tar and produces higher yield and concentration of hydrogen. However, C-2 is capable of obtaining higher exergy efficiency and lower exergy loss per mole of H₂ production. C-3 theoretically has greater process performances, but it has disadvantages in tar conversion in practical applications. The appropriate gasification temperature (T_G) are in the range of 700–750 °C and the appropriate mass ratio of steam to biomass (S/B) are in the range of 0.6–0.8 for C-1 and C-3; the corresponding parameters for C-2 are in the ranges of 650–700 °C and 0.7–0.8, respectively.     

Experimental study of wood char gasification kinetics in fluidized beds

During gasification two steps take place. The first one is pyrolysis and the second one is gasification of the char that remains back after pyrolysis. The second step is slower than the first one, so this step is the limiting factor in designing fluidized beds. Kinetic data for designing fluidized beds are necessary. The paper describes gravimetric measurements directly applied to fluidized bed with large sample sizes. The samples are char of 6 mm wood pellets and 10–40 mm wood cubes in order to directly measure ”apparent kinetics”. The parameters examined in this paper are particle size, product gases (= hydrogen) in the gasification medium, type of wood and differences in CO₂/steam gasification. The results are presented as Arrhenius diagrams and half-value period diagrams. The most important parameters are the temperature and product gases (hydrogen) in the gasification agent. The particle size seems to be less important for large wood particles as the measurements do not show significant differences for gasifying char of wood cubes 10–40 mm. The half-value periods for gasification of char from wood cubes (10 mm - 40 mm) with 100% steam at atmospheric pressure lie between 1000 s at 1023 K and 300 s at 1173 K. For char of 6 mm wood pellets the half-value periods lie between 1900 s at 1023 K and 250 s at 1173 K. The reaction is most likely in pore diffusion regime.     

Investigation of a multi-generation system using a hybrid steam biomass gasification for hydrogen, power and heat

In this paper, an integrated process of steam biomass gasification and a solid oxide fuel cell (SOFC) is investigated energetically to evaluate both electrical and energy efficiencies. This system is conceptualized as a combined system, based on steam biomass gasification and with a high temperature, pressurized SOFC. The SOFC system uses hydrogen obtained from steam sawdust gasification. Due to the utilization of the hydrogen content of steam in the reforming and shift reaction stages, the system efficiencies reach appreciable levels. This study essentially investigates the utilization of steam biomass gasification derived hydrogen that was produced from an earlier work in a system combines gasifier and SOFC to perform multi-duties (power and heat). A thermodynamic model is developed to explore a combination of steam biomass gasification, which produces 70–75 g of hydrogen/kg of biomass to fuel a planar SOFC, and generate both heat and power. Furthermore, processes are emerged in the system to increase the hydrogen yield by further processing the rest of gasification products: carbon monoxide, methane, char and tar. The conceptualized scheme combines SOFC operates at 1000 K and 1.2 bar and gasifier scheme based on steam biomass gasification which operates close to the atmospheric pressure, a temperature range of 1023–1423 K and a steam-biomass ratio of 0.8 kmol/kmol. A parametric study is also performed to evaluate the effect of various parameters such as hydrogen yield, air flow rate etc. on the system performance. The results show that SOFC with an efficiency of 50.3% operates in a good fit with the steam biomass gasification module with an efficiency, based on hydrogen yield, of 55.3%, and the overall system then works efficiently with an electric efficiency of ∼82%.     

Novel hydrogen‐rich gas production by steam gasification of biomass in a research‐scale rotary tubular helical coil gasifier

The concept of biomass steam gasification offers platform for production (i) of hydrogen, (ii) hydrocarbons and (iii) value added chemicals. Majority of these developments are either in nascent or in pilot/demonstration stage. In this context, there exists potential for hydrogen production via biomass steam gasification. Gaseous products of biomass steam gasification consist of large percentage of CO, CH₄ and other hydrocarbons, which can be converted to hydrogen through water‐gas‐shift reaction, steam reforming and cracking respectively. Although there are many previous research works showing the potential of production of hydrogen from biomass in a two stage process, challenges remain in extended biomass and char gasification so as to reduce the amount of carbon in the residual char as well as improve conversion of heavy hydrocarbon condensates to hydrogen rich gas. In the current work, the characteristics of biomass steam gasification in an in‐house designed rotary tubular helical coil reactor at temperatures less than 850 °C, in the presence of superheated steam, were presented. The objectives were to obtain high carbon conversion in the primary biomass steam gasification step (upstream) and high product gas yield and hydrogen yield in the secondary fixed bed catalytic step (downstream). The influence of temperature, steam‐to‐biomass ratio and residence time on product gas yield in the rotary tubular helical coil gasifier was studied in detail using one of the abundantly available biomass sources in India‐rice husk. Further, enhancement of product gas yield and hydrogen yield in a fixed bed catalytic converter was studied and optimized. In the integrated pathway, a maximum gas yield of 1.92 Nm³/kg moisture‐free biomass was obtained at a carbon conversion efficiency of 92%. The maximum hydrogen purity achieved under steady state conditions was 53% by volume with a hydrogen yield of 91.5 g/kg of moisture‐free biomass. This study substantiates overall feasibility of production of high value hydrogen from locally available biomass by superheated steam gasification followed by catalytic conversion. Copyright © 2016 John Wiley & Sons, Ltd.     

Steam-gasification of biomass with CaO as catalyst for hydrogen-rich syngas production

Biomass is extensively considered as a feed-stock for bio-chemicals and bio-fuels production. Among all options for the utilization of biomass, gasification process is more popular because of its environmental advantages. In this study, biomass gasification with CO₂ removal by CaO sorbent was simulated by using a commercial simulator. The model accuracy was validated with reported results from steam only gasification of biomass in presence of CaO. The system was evaluated through tar yield, carbon conversion, gas quality and H₂ yield by varying the reaction temperature, steam flow rate and CaO flow rate. The hydrogen yield enhanced slightly from 187.32 ml/g to 198.49 ml/g with the increase of CaO/B from 1.0 to 1.5. However, a further enhancement in CaO/B from 1.5 to 2 sharply enhanced the hydrogen yield approximately 1.55 times (from 198.49 ml/g to 308.54 ml/g).     

Reduction of tars by dolomite cracking during two-stage gasification of olive cake

The effective implementation of biomass gasification has to overcome some difficulties such as the minimization of tars. On the other hand, with a proper design of experimental conditions, biomass gasification can be directed towards the production of hydrogen. The aim of the present study was to investigate the use of dolomite as catalyst to improve tar removal and hydrogen production by a two-stage steam gasification process, using olive cake as raw material. Fixing the olive cake gasification conditions on the first reactor (900 °C, steam flow rate of 190 mg min⁻¹, O₂ flow rate of 7.5 cm³ min⁻¹), the cracking of tars was prompted by: a) steam gasification (steam flow rate in the range 40-190 mg min⁻¹) at 1000 °C, b) catalytic gasification, using dolomite (5% wt.). It was found that increasing steam flow rate up to 110 mg min⁻¹ involves an increase in hydrogen fraction due to the enhancement of water gas and water gas shift reactions. Also, the influence of dolomite was studied at 800 and 900 °C in a second reactor, finding better results at 800 °C, which gave an hydrogen fraction of 0.51.     

Exergy analysis of hydrogen production from steam gasification of biomass: A review

Exergy analysis of hydrogen production from steam gasification of biomass was reviewed in this study. The effects of the main parameters (biomass characteristics, particle size, gasification temperature, steam/biomass ratio, steam flow rate, reaction catalyst, and residence time) on the exergy efficiency were presented and discussed. The results show that the exergy efficiency of hydrogen production from steam gasification of biomass is mainly determined by the H₂ yield and the chemical exergy of biomass. Increases in gasification temperatures improve the exergy efficiency whereas increases in particle sizes generally decrease the exergy efficiency. Generally, both steam/biomass ratio and steam flow rate initially increases and finally decreases the exergy efficiency. A reaction catalyst may have positive, negative or negligible effect on the exergy efficiency, whereas residence time generally has slight effect on the exergy efficiency.     

Two-step steam pyrolysis of biomass for hydrogen production

In this study, different char based catalysts were evaluated in order to increase hydrogen production from the steam pyrolysis of olive pomace in two stage fixed bed reactor system. Biomass char, nickel loaded biomass char, coal char and nickel or iron loaded coal chars were used as catalyst. Acid washed biomass char was also tested to investigate the effect of inorganics in char on catalytic activity for hydrogen production. Catalysts were characterized by using Brunauer–Emmet–Teller (BET) method, X-ray diffraction (XRD) analyzer, X-ray fluorescence (XRF) and thermogravimetric analyzer (TGA). The results showed that the steam in absence of catalyst had no influence on hydrogen production. Increase in catalytic bed temperature (from 500 °C to 700 °C) enhanced hydrogen production in presence of Ni-impregnated and non-impregnated biomass char. Inherent inorganic content of char had great effect on hydrogen production. Ni based biomass char exhibited the highest catalytic activity in terms of hydrogen production. Besides, Ni and Fe based coal char had catalytic activity on H₂ production. On the other hand, the results showed that biomass char was not thermally stable under steam pyrolysis conditions. Weight loss of catalyst during steam pyrolysis could be attributed to steam gasification of biomass char itself. In contrast, properties of coal char based catalysts after steam pyrolysis process remained nearly unchanged, leading to better thermal stability than biomass char.     

Hydrogen-rich gas production from biomass air and oxygen/steam gasification in a downdraft gasifier

Biomass gasification is an important method to obtain renewable hydrogen. However, this technology still stagnates in a laboratory scale because of its high-energy consumption. In order to get maximum hydrogen yield and decrease energy consumption, this study applies a self-heated downdraft gasifier as the reactor and uses char as the catalyst to study the characteristics of hydrogen production from biomass gasification. Air and oxygen/steam are utilized as the gasifying agents. The experimental results indicate that compared to biomass air gasification, biomass oxygen/steam gasification improves hydrogen yield depending on the volume of downdraft gasifier, and also nearly doubles the heating value of fuel gas. The maximum lower heating value of fuel gas reaches 11.11 MJ/N m³ for biomass oxygen/steam gasification. Over the ranges of operating conditions examined, the maximum hydrogen yield reaches 45.16 g H₂/kg biomass. For biomass oxygen/steam gasification, the content of H₂ and CO reaches 63.27–72.56%, while the content of H₂ and CO gets to 52.19–63.31% for biomass air gasification. The ratio of H₂/CO for biomass oxygen/steam gasification reaches 0.70–0.90, which is lower than that of biomass air gasification, 1.06–1.27. The experimental and comparison results prove that biomass oxygen/steam gasification in a downdraft gasifier is an effective, relatively low energy consumption technology for hydrogen-rich gas production.     

Steam reforming of gasification-derived tar for syngas production

In this study, the steam reforming of tar was catalyzed by dolomite, Ni/dolomite, and Ni/CeO₂ for syngas production under different reaction temperature and weight hourly space velocity (WHSV, h⁻¹). The tar was the major side product from the biomass gasification.     

Improving the performance of fluidized bed biomass/waste gasifiers for distributed electricity: A new three-stage gasification system

Methods to increase the conversion of char and tar in fluidized bed gasifiers (FBG) are discussed, with the focus on small to medium-size biomass/waste gasifiers for power production (from 0.5 to 10 MW_e). Optimization of such systems aims at (i) maximizing energy utilization of the fuel (maximizing char conversion), (ii) minimizing secondary treatment of the gas (by avoiding complex tar cleaning), and (iii) application in small biomass-to-electricity gasification plants. The efficiency of various measures to increase tar and char conversion within a gasification reactor (primary methods) is discussed. The optimization of FBG by using in-bed catalysts, by addition of steam and enriched air as gasification agent, and by secondary-air injection, although improving the process, is shown to be insufficient to attain the gas purity required for burning the gas in an engine to produce electricity. Staged gasification is identified as the only method capable of reaching the targets mentioned above with reasonable simplicity and cost, so it is ideal for power production. A promising new stage gasification process is presented. It is based on three stages: FB devolatilization, non-catalytic air/steam reforming of the gas coming from the devolatilizer, and chemical filtering of the gas and gasification of the char in a moving bed supplied with the char generated in the devolatilizer. Design considerations and comparison with one-stage FBG are discussed.     

Hydrogen-rich gas production by air–steam gasification of rice husk using supported nano-NiO/γ-Al2O3 catalyst

The air–steam catalytic gasification of rice husk for hydrogen-rich gas production was experimentally investigated in a combined fixed bed reactor with the newly developed nano-NiO/γ-Al₂O₃ catalyst. A series of experiments have been performed to explore the effects of catalyst presence, catalytic reactor temperature, the equivalence ratio (ER), and steam to biomass ratio (S/B) on the composition and yield of gasification gases. The experiments demonstrated that the developed nano-NiO/γ-Al₂O₃ catalyst had a high activity of cracking tar and hydrocarbons, upgrading the gas quality, as well as yielding a high hydrogen production. Catalytic temperature was crucial for the overall gasification process, a higher temperature contributed to more hydrogen production and gas yield. Varying ER demonstrated complex effects on rice husk gasification and an optimal value of 0.22 was found in the present study. Compared with biomass catalytic gasification under air only, the introduction of steam improved the gas quality and yield. The steam/biomass ratio of 1.33 was found as the optimum operating condition in the air–steam catalytic gasification.     

Tar evolution profiles obtained from gasification of biomass and coal

The tar content of the product gases from gasification of biomass is one of the major factors affecting the subsequent process stages. In this work, evolution profiles of the main tar constituents, i.e. benzene, toluene, indene, naphthalene and phenol were obtained during about 1 h gasification runs of biomass and coal in a pressurised fluidised-bed at 700 and 900°C, 0.4 MPa. Sampling and analysis was achieved, using the solid-phase adsorption (SPA) method, previously developed in our laboratory. Our main objectives were: (1) to illustrate the usefulness of the SPA method; (2) to shed new light on the main factors governing tar evolution. It was found that temperature and the type of feedstock used mainly affected tar yields. For both biomass and coal the concentration of tar products decreased with increasing run time at a rate that was fastest initially. This behaviour, which was much more pronounced for coal, provides evidence that char catalytically affects tar evolution. Accordingly, char accumulates in the bed to a various extent depending on fuel and gradually approaching steady state. Biomass char, contrary to coal char, is readily oxidised during gasification, and thus only small steady-state amounts are available to catalyse tar cracking reactions.     

High temperature steam-only gasification of woody biomass

We have studied a high temperature steam gasification process to generate hydrogen-rich fuel gas from woody biomass. In this study, the performance of the gasification system which employs only high temperature steam exceeding 1200 K as the gasifying agent was evaluated in a 1.2 ton/day-scale demonstration plant. A numerical analysis was also carried out to analyze the experimental results. Both the steam temperature and the molar ratio of steam to carbon (S/C ratio) affected the reaction temperature which strongly affects the gasified gas composition. The H₂ fraction in the produced gas was 35–55 vol.% at the outlet of the gasifier. Under the experimental conditions, S/C ratio had a significant effect on the gas composition through the dominant reaction, water–gas shift reaction. The tar concentration in the produced gas from the high temperature steam gasification process was higher than that from the oxygen-blown gasification processes. The highest cold gas efficiency was 60.4%. However, the gross cold gas efficiency was 35%, which considers the heat supplied by high temperature steam. The ideal cold gas efficiency of the whole system with heat recovery processes was 71%.     

Production of hydrogen enriched syngas from municipal solid waste gasification with waste marble powder as a catalyst

Marble processing leads to the production of high amount of waste marble powder (WMP) as a byproduct, which can be a potential health risk and has hazardous impacts on the surrounding environment. However, marble is composed of calcite making it suitable for the calcium-based catalyst. Moreover, no study has been carried out to utilize this WMP in municipal solid waste (MSW) gasification process. Therefore, there is a need to address its utilization as a potential catalyst/sorbent in the gasification of municipal solid waste (MSW). A laboratory scale batch-type fixed bed reactor was used to study the effect of WMP addition on the CO₂ adsorption, steam reforming capability and char gasification in the presence of steam. Produced gas composition, gas yield, carbon conversion efficiency and tar yield were examined at different WMP to MSW ratios. Effect of temperature and steam rate varying from 700 to 900 °C and 2.5–10 ml/min respectively were also considered in this study. WMP showed a good capacity towards hydrogen enriched syngas production as well as CO₂ adsorption and tar reforming. The H₂ concentration increased significantly with an increase in the WMP to MSW mass ratio, while CO₂ decreased. A significant effect of temperature and steam rate was also observed on the produced gas composition, gas yield, and tar content. This study helps us to understand the effect of WMP addition in MSW gasification process and thus assists in the industrial application.     

Integrated drying and gasification of wet microalgae biomass to produce H2 rich syngas – A thermodynamic approach by considering in-situ energy supply

A novel integrated drying and gasification of microalgae wet biomass process, involving a chemical-looping combustion (CLC) option to supply energy, is developed using Aspen Plus. The integrated gasification system consists of four primary units, including (i) a wet biomass drying unit, (ii) the gasification system, (iii) the CLC section, and (iv) the gas purification process. The model shows a good accuracy (relative error < 10%) in predicting the product compositions as compared to the experimental results under consistent operating conditions. The performance of the integrated gasification system is evaluated using Spirulina microalgae at various moisture contents (0–45 wt%). The effect of gasifying agents O₂/steam and the fraction of the produced char used in the CLC section on the gasification performance is also evaluated. The tar is successfully reformed into syngas in the pyrolysis stage by adjusting the O₂ flow rate. The C (char) to CLC provides to a positive effect on the syngas composition, particularly for gasification of wet biomass, but brings an adverse impact on the yield of the syngas product. The integration of the CLC process and CO₂ absorber in the gasification system provides high-quality syngas by removing CO₂. The separated pure CO₂ can be used as a feedstock for other chemical industries.     

Experimental simulate on hydrogen production of different coals in underground coal gasification

Research on hydrogen production from coal gasification is mainly focused on the formation of CO and H₂ from coal and water vapor in high-temperature environments. However, in the process of underground coal gasification, the water gas shift reaction of low-temperature steam will absorb a lot of heat, which makes it difficult to maintain the combustion of coal seams in the process of underground coal gasification. In order to obtain high-quality hydrogen, a pure oxygen-steam gasification process is used to improve the gasification efficiency. And as the gasification surface continues to recede, the drying, pyrolysis, gasification and combustion reactions of underground coal seams gradually occur. Direct coal gasification can't truly reflect the process of underground coal gasification. In order to simulate the hydrogen production laws of different coal types in the underground gasification process realistically, a two-step gasification process (pyrolysis of coal followed by gasification of the char) was proposed to process coal to produce hydrogen-rich gas. First, the effects of temperature and coal rank on product distribution were studied in the pyrolysis process. Then, the coal char at the final pyrolysis temperature of 900 °C was gasified with pure oxygen-steam. The results showed that, the hydrogen production of the three coal chars increased with the increase of temperature during the pyrolysis process, the hydrogen release from Inner Mongolia lignite and Xinjiang long flame coal have the same trend, and the bimodality is obvious. The hydrogen release in the first stage mainly comes from the dehydrogenation of the fat side chain, and the hydrogen release in the second stage mainly comes from the polycondensation reaction in the later stage of pyrolysis, and the pyrolysis process of coal contributes 15.81%–43.33% of hydrogen, as the coal rank increases, the hydrogen production rate gradually decreases. In the gasification process, the release of hydrogen mainly comes from the water gas shift reaction, the hydrogen output is mainly affected by the quality and carbon content of coal char. With the increase of coal rank, the hydrogen output gradually increases, mainly due to the increasing of coal coke yield and carbon content, The gasification process of coal char contributes 56.67–84.19% of hydrogen, in contrast, coal char gasification provides more hydrogen. The total effective gas output of the three coal chars is 0.53–0.81 m³/kg, the hydrogen output is 0.3–0.43 m³/kg, and the percentage of hydrogen is 53.08–56.60%. This study shows that two-step gasification under the condition of pure oxygen-steam gasification agent is an efficient energy process for hydrogen production from underground coal gasification.     

Thermodynamic analysis of combined unit of biomass gasifier and tar steam reformer for hydrogen production and tar removal

A combined unit of biomass gasifier and tar steam reformer (CGR) was proposed in this study to achieve simultaneous tar removal and increased hydrogen production. Tar steam reforming calculations based on thermodynamic equilibrium were carried out by using Aspen Plus software. Thermodynamic analysis reveals that when selecting appropriate operating conditions, exothermic heat available from the gasifier could sufficiently supply to the heat-demanding units including feed preheaters, steam generator and reformer. The effects of gasification temperature (T_gs), reforming temperature (T_ref) and steam-to-biomass ratio (S:BM) on percentages of tar removal and improvement of H₂ production were investigated. It was reported that the CGR system can completely remove tar and increase H₂ production (1.6 times) under thermally self-sufficient condition. The increase of H₂ production is mainly via the water–gas shift reaction.     

Influence of catalyst and temperature on gasification performance of pig compost for hydrogen-rich gas production

The catalytic steam gasification of pig compost (PC) for hydrogen-rich gas production was conducted in a fixed-bed reactor. The influence of the catalyst and reactor temperature on yield and product composition was studied at the temperature range of 700–850 °C, for weight hourly space velocity (WHSV) in the range of 0.30–0.60 h⁻¹. The results indicate that the developed NiO on modified dolomite (NiO/MD) catalyst reveals better catalytic performance on the tar elimination and hydrogen yield than calcined MD or NiO/γ-Al₂O₃ catalyst. Meanwhile, the lower WHSV and higher reactor temperature can contribute to more hydrogen production and gas yield. Moreover, the char from catalytic steam gasification of PC has a highest ash content of 75.84% at 850 °C. In conclusion, pig compost is a potential candidate for hydrogen gas production through catalytic steam gasification technology.