Desulfurization and tar reforming of biogenous syngas over Ni/olivine in a decoupled dual loop gasifier

For the production of bio-SNG (substitute natural gas) from syngas of biomass steam gasification, trace amounts of sulfur and tar compounds in raw syngas must be removed. In present work, biomass gasification and in-bed raw gas upgrading have been performed in a decoupled dual loop gasifier (DDLG), with aggregation-resistant nickel supported on calcined olivine (Ni/olivine) as the upgrading catalyst for simultaneous desulfurization and tar elimination of biogenous syngas. The effects of catalyst preparation, upgrading temperature and steam content of raw syngas on sulfur removal were investigated and the catalytic tar reforming at different temperatures was evaluated as well. It was found that 850 °C calcined Ni/olivine was efficient for both inorganic-sulfur (H₂S) and organic-sulfur (thiophene) removal at 600–680 °C and the excellent desulfurization performance was maintained with wide range H₂O content (27.0–40.7%). Meanwhile, tar was mostly eliminated and H₂ content increased much in the same temperature range. The favorable results indicate that biomass gasification in DDLG with Ni/olivine as the upgrading bed material could be a promising approach to produce qualified biogenous syngas for bio-SNG production and other syngas-derived applications in electric power, heat or fuels.     

High quality H2-rich syngas production from pyrolysis-gasification of biomass and plastic wastes by Ni–Fe@Nanofibers/Porous carbon catalyst

To produce the high quality H₂-rich syngas from biomass and plastic wastes, a two-stage pyrolysis-gasification system involving pyrolysis and catalytic gasification is considered as a suitable route. Generally, synthesis of highly active, low cost and coke-resistant catalyst for tar cracking is the key factor. A series of monometallic catalysts of Ni@CNF/PCs and Fe@CNF/PCs and the bimetallic Ni–Fe@CNF/PCs catalyst were prepared by a simple one-step pyrolysis approach for high quality syngas production from pyrolysis-gasification of biomass and plastic wastes. The results indicated that the bimetallic Ni–Fe@CNF/PCs catalyst appeared as the optimal catalyst in affording the best compromise between catalytic activity and stability with the existence of the excellent dispersibility of the Fe0.64Ni0.36 alloy nanoparticles and the carbon nanofibers/porous carbon composite structure. In addition, the optimal operation conditions of biomass/plastic ratio of 1/2 and gasification temperature of 700 °C were observed for the bimetallic Ni–Fe@CNF/PCs catalyst to play best roles in the H₂-rich syngas quality, with up to 33.66 mmol H₂/g biomass, and tar yields as low as 5.66 mg/g.     

Methanation of syngas from biomass gasification: An overview

Traditional fossil fuel overuse could lead to global warming and environmental pollution. As a renewable energy, biomass energy is a sustainable and low pollution carbon energy, which has a wide range of sources. Syngas production from biomass thermochemical conversion is a promising technology to realize effective utilization of the renewable energy. Syngas produced from gasification could be further converted into value-added chemicals via the method of Fischer-Tropsch synthesis. Syngas and CO₂ methanation could transform renewable energy into feasible transport and high-density energy. However, tar formation and catalyst deactivation are the main problem during the biomass gasification and methanation. This review sheds light on the development of biomass gasification and syngas methanation. Firstly, we presented the common reactors and some other factors during gasification. Secondly, we provide a comprehensive introduction of the advanced active catalyst for gasification and syngas methanation. Finally, some representative large-scale and commercial plants and companies for biomass gasification were compared and discussed in details. Then the prospective developments in combination of gasification and methanation were concluded to give an outlook for biomass gasification and its downstream development.     

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.     

Experimental analysis of air-steam gasification of biomass with coal-bottom ash

Biomass gasification is an attractive option for producing high-quality syngas (H₂+CO) due to its environmental advantages and economic benefits. However, due to some technical problems such as tar formation, biomass gasification has not yet been able to achieve its purpose. The purpose of this work was to study the catalytic activity of coal-bottom ash for fuel gas production and tar elimination. Effect of gasification parameters including reaction temperature (700–900 °C), equivalence ratio, EQR (0.15–0.3) and steam-to-biomass ratio, SBR (0.34–1.02) and catalyst loading (5.0–13 wt %) on gas distribution, lower heating value (LHV) of gas steam, tar content, gas yield and H₂/CO ratio was studied. The tar content remarkably decreased from 3.81 g/Nm³ to 0.97 g/Nm³ by increasing char-bottom ash from 5.0 wt% to 13.0 wt%. H₂/CO significantly increased from 1.12 to 1.54 as the char-bottom ash content in the fuel increased from 5.0 wt% to 13.0 wt%.     

Char and char-supported nickel catalysts for secondary syngas cleanup and conditioning

Tars in biomass gasification systems need to be removed to avoid damaging and clogging downstream pipes or equipment. In this study, Ni-based catalysts were made by mechanically mixing NiO and char particles at various ratios. Catalytic performance of the Ni/char catalysts was studied and compared with performance of wood char and coal char without Ni for syngas cleanup in a laboratory-scale updraft biomass gasifier. Reforming parameters investigated were reaction temperature (650–850 °C), NiO loading (5–20% of the weight of char support), and gas residence time (0.1–1.2 s). The Ni/coalchar and Ni/woodchar catalysts removed more than 97% of tars in syngas at 800 °C reforming temperature, 15% NiO loading, and 0.3 s gas residence time. Analysis of syngas composition indicated that concentrations of H₂ and CO in syngas significantly. Furthermore, performance of the Ni/coalchar catalyst was continuously tested for 8 h. There was slight deactivation of the catalyst in the early stage of tar/syngas reforming; however, the catalyst was able to stabilize soon after. It was concluded that chars especially coal char can be an effective and inexpensive support of NiO for biomass gasification tar removal and syngas conditioning.     

Hydrogen‐rich gas production from catalytic gasification of pine sawdust over Fe‐Ce/olivine catalyst

In order to improve hydrogen production and reduce tar generation during the biomass gasification, a catalyst loaded Fe‐Ce using calcined olivine as the support (Fe‐Ce/olivine catalysts) was prepared through deposition‐precipitation method. The characteristics of catalysts were determined by XRF, BET, XRD, and FTIR. Syngas yield, hydrogen yield, and tar yield were used to evaluate the catalyst activity. Meanwhile, the stability of catalysts was also studied. The results showed that the specific surface area and pore volume of olivine after calcined at high temperature were improved which was beneficial for the load of metals. α‐Fe₂O₃ and CeO₂ were the main active component of Fe‐Ce/olivine catalyst. The Fe‐Ce/olivine catalyst displayed a good performance on the catalytic gasification of pine sawdust with a syngas yield of 0.93 Nm³/kg, H₂ yield of 21.37 mol/kg, and carbon conversion rate of 55.14% at a catalytic temperature and gasification temperature of 800°C. Meanwhile, the Fe‐Ce/olivine catalyst could maintain a good stability after 150 minutes used.     

Biomass to hydrogen-rich syngas via tar removal from steam gasification with La1-XCeXFeO3/dolomite as a catalyst

Biomass gasification produces hydrogen, which is a clean and promising technology. One of the most important aspects of the biomass gasification process is choosing the right catalyst. In this study, 10% La_1-XCe_XFeO₃/Dolomite (X = 0,0.2,0.4,0.6,0.8) synthesized using the sol-gel method was used as a catalyst in biomass gasification for the production of hydrogen-rich syngas. Gasification tests were carried out in a fixed bed reactor. The effects of an elemental substitution in LaFeO₃, temperature on the product were examined. Ce-substitution boosted the activity of LaFeO₃/DOL according to the data. Among the prepared catalysts, La_0.8Ce_0.2FeO₃/DOL performed the best, yielding a greater H₂ production and tar with a higher naphthalene concentration. As the temperature rises, so does the H₂ yield, at 850 °C, the highest H₂ yield is 0.69Nm³/Kg. Furthermore, the aromatization of phenols in tar is more likely to occur at high temperatures.     

Chemical looping dry reforming of benzene as a gasification tar model compound with Ni- and Fe-based oxygen carriers in a fluidized bed reactor

Gasification tar during a fluidized bed operation impedes syngas utilization in downstream applications. Among tar constituents sampled during biomass gasification, benzene was the most abundant species. Thus, benzene was used as a model compound for chemical looping dry reforming (CLDR) over iron (Fe) and nickel (Ni) metals impregnated on silicon carbide (SiC) in a lab-scale fluidized bed reactor to convert it into hydrogen and carbon monoxide (H₂ and CO). A high benzene conversion rate (>90%) was observed at a higher experimental temperature (above 730 °C). Catalytic conversion of benzene using NiFe/SiC catalyst resulted in higher H₂ production whereas higher levels of CO were produced with Fe/SiC catalyst at an elevated temperature. Control experiments using an empty bed and SiC bed showed the formation of both the biphenyls and excessive carbon deposits. Air oxidation was also performed for the regeneration of oxygen carrier during the chemical looping operation.     

The performance of nickel-loaded lignite residue for steam reforming of toluene as the model compound of biomass gasification tar

Tars should be removed from biomass gasification systems so as not to damage or clog downstream pipes or equipment. In this paper, lignite insoluble residue (LIR) after extraction of humic acids was used as the support to prepare a nickel-loaded LIR (Ni/LIR) catalyst. This novel catalyst Ni/LIR was tested in steam reforming of toluene as a model compound of biomass tar conducted in a laboratory-scale fixed bed reactor. When compared to the reactions without catalyst or with Ni/Al₂O_3, Ni/LIR was confirmed as an active catalyst for toluene conversion at a relatively low temperature of 900 K. The investigated reforming parameters during the experiments in this research were selected as reaction temperature at a range of 850–950 K, steam/carbon molar ratio at a range of 2–5 mol/mol, and a space velocity from 1696 to 3387 h^?1. It was concluded that, under optimum conditions, significant amount of syngas yields, acceptable Ni/LIR consumption and more than 95% of toluene conversion can be obtained from the biomass Ni/LIR catalytic gasification system.     

Experimental study of torrefied pine as a gasification fuel using a bubbling fluidized bed gasifier

Torrefied biomass has higher C/O ratio, resulting in improved heating value and reduced hygroscopic nature of the biomass, thus enabling longer storage times. In the southeastern United States, pine is has been identified as a potential feedstock for energy production. The objective of this study was to understand the performance of torrefied pine as a gasification fuel in a bench-scale bubbling fluidized bed gasifier. The gasification of torrefied pine was carried out at 790, 935 and 1000 °C and three equivalence ratios (ERs: 0.20, 0.25 and 0.30). The effect of process variables were studied based on i) products yield, ii) syngas composition iii) syngas energy content, and iv) contaminants. The mean concentration of CO increased with an increase in temperature, but was not statistically significant. On the other hand, H₂ concentration increased whereas CH₄ concentration decreased significantly with an increase in temperature from 790 to 935 °C. Further, with an increase in ER from 0.20 to 0.30, only CO₂ concentrations increased in the syngas. Results from torrefied pine were compared with raw pine gasification, and it was observed that torrefied pine gasification led to much higher char yield (more than twice) than pine; however, it produced less than half as much tar.     

Enhancement of the quality of syngas from catalytic steam gasification of biomass by the addition of methane/model biogas

In this study, methane and model biogas were added during the catalytic steam gasification of pine to regulate the syngas composition and improve the quality of syngas. The effects of Ni/γ-Al₂O₃ catalyst, steam and methane/model biogas on H₂/CO ratio, syngas yield, carbon conversion rate and tar yield were explored. The results indicated that the addition of methane/model biogas during biomass steam gasification could increase the H₂/CO ratio to about 2. Methane/model biogas, steam and Ni/γ-Al₂O₃ catalyst significantly affected the quality of syngas. High H₂ content syngas with H₂/CO ratio of about 2, biomass carbon conversion >85% and low tar yield was achieved under the optimum condition: S/C = 1.5, α = 0.2 and using Ni/γ-Al₂O₃ catalyst. According to ANOVA, methane and catalyst were the key influencing factors of the H₂/CO ratio and syngas yield, and the tar yield mainly depended on the Ni/γ-Al₂O₃ catalyst. Biogas, as a more environmentally friendly material than methane, can also regulate the composition of syngas co-feeding with biomass.     

The aluminum silicate catalyst effect on efficiency of energy yield in gasification of paper-reject sludge

This research investigated the mineral aluminum silicate catalyst effect on the enhancement of energy yield efficiency and reduction of the tar yield concentration in the gasification of paper-reject sludge. Experimental results indicated that the energy yield efficiency is enhanced by the tested mineral catalyst. When gasification temperature operated at 600 °C, the lower heating value (LHV) of syngas increased significantly from 8.66 MJ/Nm³ to 13.38 MJ/Nm³ with an increase in aluminum silicate catalyst addition from 0% to 20%. The energy density of syngas also increased from 0.53 to 0.82. This implied that the energy utilization of syngas produced by a low temperature catalytic gasification could increase approximately 1.5 times the energy content of paper-reject sludge. The tar reduction efficiency could reach approximately 50% which was also proportional to the catalyst addition ratio. In summary, the aluminum silicate catalyst can help to improve the efficiency of tar reduction and energy yield in a low temperature catalytic gasification of paper-reject sludge.     

Steam reforming of hot gas from gasified wood types and miscanthus biomass

The reforming of hot gas generated from biomass gasification and high temperature gas filtration was studied in order to reach the goal of the CHRISGAS project: a 60% of synthesis gas (as x(H₂)+ x(CO) on a N₂ and dry basis) in the exit gas, which can be converted either into H₂ or fuels. A Ni-MgAl₂O₄ commercial-like catalyst was tested downstream the gasification of clean wood made of saw dust, waste wood and miscanthus as herbaceous biomass. The effect of the temperature and contact time on the hydrocarbon conversion as well as the characterization of the used catalysts was studied. Low (<600 °C), medium (750°C–900 °C) and high temperature (900°C–1050 °C) tests were carried out in order to study, respectively, the tar cracking, the lowest operating reformer temperature for clean biomass, the methane conversion achievable as function of the temperature and the catalyst deactivation. The results demonstrate the possibility to produce an enriched syngas by the upgrading of the gasification stream of woody biomass with low sulphur content. However, for miscanthusthe development of catalysts with an enhanced resistance to sulphur poison will be the key point in the process development.     

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.     

Recent experimental advances on the utilization of biochar as a tar reforming catalyst: A review

Biomass gasification to form syngas is a promising renewable energy production process. Here, biomass is exposed to high temperatures in an oxygen-controlled environment where volatiles react to form components of syngas that can be used for energy or chemical production. A limitation to the use of gasification is the generation of tars that condense in downstream equipment causing damage and halting production. Currently tars are removed by physical, thermal, or catalytic processes, all high-cost options. On the other hand, biochar is produced as a solid by-product of gasification, characterized by high surface area, desirable adsorption properties, and relatively low cost. This review details the use of biochar as a catalyst to reform tars, while highlighting recent experimental advances in evaluating the effects of biomass composition, gasification conditions, and pre-treatment and post-treatment options to improve catalytic function. It discusses tar degradation mechanisms and catalyst deactivation and recommends further areas for research.     

Biomass thermochemical conversion: A review on tar elimination from biomass catalytic gasification

Biomass is promising renewable energy because of the possibility of value-added fuels production from biomass thermochemical conversion. Among the thermochemical conversion technology, gasification could produce the H₂-rich syngas then into value-added chemicals via F-T (Fischer-Tropsch) synthesis. However, a variety of difficulties, such as tar formation, reactors impediment, complex tar cracked mechanism, etc. make it difficult to develop for further application. This paper sheds light on the developments of biomass thermochemical conversion, tar classifications, tar formation, and elimination methods. Secondly, we provide a comprehensive the state-of-the-art technologies for tar elimination, and we introduce some advanced high activity catalysts. Furthermore, many represent tar models were employed for explanation of the tar-cracked pathway, and real tar-cracked mechanism was proposed. Following this, some operational conditions and effective gasified models were concluded to give an instruction for biomass catalytic gasification.     

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.     

Investigation of syngas exergy value and hydrogen concentration in syngas from biomass gasification in a bubbling fluidized bed gasifier by using machine learning

In this study, an artificial neural network (ANN) model as a machine learning method has been employed to investigate the exergy value of syngas, where the hydrogen content in syngas reached maximum in bubbling fluidized bed gasifier which is developed in Aspen Plus® and validated from experimental data in literature. Levenberg-Marquardt algorithm has been used to train ANN model, where oxygen, hydrogen and carbon contents of sixteen different biomass, gasification temperature, steam and fuel flow rates were selected as input parameters of the model. Moreover, four different biomass samples, which hadn't been used in training and testing, have been used to create second validation. The hydrogen mole fraction of syngas was also evaluated at the different steam to fuel ratio and gasification temperature and the exergy value of syngas at the point where the hydrogen content in syngas reached maximum were estimated with low relative error value.     

Construction of high-performance NiCe-MOF derived structured catalyst for steam reforming of biomass tar model compound

High-performance and inexpensive catalysts play a large role in effective removal of biomass tar produced during biomass gasification. In this study, raw wood, with long, through, but distorted channels and a low tortuosity, was selected as a support. A layered NiCe-metal organic framework (NiCe-MOF) was grown in-situ on the surface of raw wood microchannels by using abundant surface hydroxide groups. Then, this catalyst was carbonized at 600 °C in a N₂ atmosphere to obtain NiCe-MOF derived catalyst/wood carbon (NiCe-MDC/WC), which was selected as a structured reactor for the steam reforming of biomass tar. NiCe-MDC/WC achieved an excellent conversion rate of approximately 99% for toluene and a high catalytic stability of 48 h at low temperature of 550 °C. Moreover, NiCe-MDC/WC showed higher catalytic performance than Ni-MDC/WC (～79%), crushed-NiCe-MDC/WC (～94%), and Ni/WC (～75%) in stability tests. These excellent results were assumed to be derived from the multilevel structure obtained from wood carbon microchannels and secondary layered MOF channels, appropriate metal-support interactions, and the presence of Ce, which could improve the dispersion of active sites and mass transfer efficiency and inhibit coke formation. Thus, such Ni-based MOF-derived structured reactors are promising for tar conversion and useful syngas production.