Modeling and parametric optimization of air catalytic co-gasification of wood-oil palm fronds blend for clean syngas (H2+CO) production

Syngas production from biomass gasification is a potentially sustainable and alternative means of conventional fuels. The current challenges for biomass gasification process are biomass storage and tar contamination in syngas. Co-gasification of two biomass and use of mineral catalysts as tar reformer in downdraft gasifier is addressed the issues. The optimized and parametric study of key parameters such as temperature, biomass blending ratio, and catalyst loading were made using Response Surface Methodology (RSM) and Artificial Neural Network (ANN) on tar reduction and syngas. The maximum H₂ was produced when Portland cement used as catalyst at optimum conditions, temperature of 900 °C, catalyst-loading of 30%, and biomass blending-ratio of W52:OPF48. Higher CO was yielded from dolomite catalyst and lowest tar content obtained from limestone catalyst. Both RSM and ANN are satisfactory to validate and predict the response for each type of catalytic co-gasification of two biomass for clean syngas production.     

Effect of calcium based catalyst on production of synthesis gas in gasification of waste bamboo chopsticks

This study investigated the effects of calcium based catalyst (calcium oxide) on variation of gas composition in catalytic gasification reaction stages by controlling the gasification temperature between 600 °C and 900 °C whilst varying a catalyst/biomass ratio from 0 to 0.2 w/w. The tested biomass generated from used bamboo chopsticks were used as the feedstock. To assess the gas composition variation, the ratio of H₂/CO, H₂/CO₂, CO/CO₂, and 3H₂/CH₄ are four important factors that affect the performance of catalytic gasification process. The maximum ratio of H₂/CO increased from 0.23 to 0.72 in the gasification temperature range between 600 °C and 900 °C and 0%–20% calcium based catalyst addition ratio. This is due to enhanced H₂ production as a result of the facilitated water–gas shift reaction. The ratios of CO/CO₂ and 3H₂/CH₄ increased significantly from 0.9 to 2.1 and from 2.6 to 4.1, respectively, when the gasification temperature increased from 600 °C to 900 °C and 20% catalyst addition ratio. Obviously, the high temperature and catalyst addition are favorable for production of CO and H₂ during gasification of tested biomass. In conclusion, the tested mineral calcium based catalyst (CaO) can help facilitating the reaction rate of partial oxidation and water–gas shift reaction, enhancing the quality of synthesis gas, and reduction of the gasification reaction time. This catalyst has potential application in gasification of waste bamboo chopsticks in the future.     

Valorisation of vegetable market wastes to gas fuel via catalytic hydrothermal processing

Residues of leek, cabbage and cauliflower from the market places as representatives of lignocellulosic biomass were processed via hydrothermal gasification to produce energy fuel. The experiments were carried out in a batch reactor at temperatures 300, 400, 500 and 600 °C and corresponding pressures varying in the range of 7.5–43 MPa. Natural mineral additives trona, dolomite and borax were used as homogenous catalysts to determine their effects on the gasification. More than 70 wt% of carbon in vegetable residue samples were detected in the gas phase after the hydrothermal gasification process at 600 °C. The addition of trona mineral further promoted the gasification reactions and as a result, less than 5 wt% carbon remained in the solid residue at the same temperature, degrading the biomass samples into gas and liquid products. The fuel gas with the highest calorific value was recorded to be 25.6 MJ/Nm³, from the hydrothermal gasification of cabbage at 600 °C, when dolomite was used as the homogeneous catalyst. The liquid products obtained in the aqueous phase were detected as organic acids, aldehydes, ketones, furfurals and phenols. The gas products were consisted of hydrogen, carbon dioxide, methane, and as minors; carbon monoxide and low molecular weight hydrocarbons (ethane, propane, etc.). Above 500 °C, all biomass samples yielded 50–55 vol% of CH₄ and H₂ while the CO₂ composition was around 40 vol% as the gas product.     

Catalytic supercritical water gasification of black liquor along with lignocellulosic biomass

Supercritical water gasification (SCWG) is a novel technology for environmental pollution management and hydrogen production from biomass and wastes. In this study, the SCWG of black liquor (BL) which is high-potential biomass and rich in alkalis was investigated. The experiments were conducted in a batch reactor at 350–400 °C, reaction time of 1–60 min, and constant concentration of 9 wt% of BL in the absence and presence of heterogeneous catalysts (3–5 wt%), lignocellulosic biomass, and formic acid (5 and 7 wt %) in three parts. First, the SCWG of BL was performed without any additive. The experimental results showed that the maximum production of H₂, CO₂, and CH₄ was obtained at the highest temperature and reaction time; 400 °C and 60 min. The hydrogen yield was also enhanced by increasing the temperature, and reached 3.51 mol H₂/kg dry ash free-black liquor (DAF-BL) at 400 °C. Reaction time increment improved the gas product and gasification efficiency up to 28.03 mmol and 21.73%, respectively. Subsequently, three heterogeneous catalysts (MnO₂, CuO, and TiO₂) were used, however 5 wt% of MnO₂ was the best catalyst, significantly improving the hydrogen yield compared to the same condition of BL gasification without a catalyst. Hydrogen yield reached 5.09 mol H₂/kg (DAF-BL) at 400 °C and the reaction time of 10 min. Finally, BL with poplar wood residue as a lignocellulosic biomass and formic acid was gasified separately and the highest hydrogen yield was obtained in the case of 5 wt% of formic acid (10.79 mol H₂/kg (DAF-BL)). Overally, SCWG dramatically reduced the chemical oxygen demand of BL to 76% using 5 wt% of formic acid.     

Release of inorganic trace elements during gasification of wood,straw, and miscanthus

The release of alkali metals, chlorine, sulphur and heavy metals during gasification of four different types of biomass was investigated. The samples were two types of wood (clean and waste wood), miscanthus, and straw. Experiments were conducted in two different setups; in a tube furnace which could be considered as batch experiments, and in an atmospheric lab scale fluidised bed reactor with continuous fuel feed. Molecular beam mass spectrometry was used for on-line analysis of the hot gas. The experimental results reveal that the release of inorganic species like HCl, KCl and H₂S is strongly dependent on other inorganic constituents in the samples, e.g. Si and Ca. In general, the release from herbaceous biomass is much higher than from woody biomass. With the exception of zinc released from miscanthus at temperatures above 900 °C, no heavy metals could be detected. The measurements were accompanied by equilibrium calculations using FactSage 5.5 and the FACT database which are in relatively good agreement with the experimental results.     

Hydrogen production enhancement using hot gas cleaning system combined with prepared Ni-based catalyst in biomass gasification

This paper investigates the hot gas temperature effect on enhancing hydrogen generation and minimizing tar yield using zeolite and prepared Ni-based catalysts in rice straw gasification. Results obtained from this work have shown that increasing hot gas temperature and applying catalysts can enhance energy yield efficiency. When zeolite catalyst and hot gas temperature were adjusted from 250 °C to 400 °C, H₂ and CO increased slightly from 7.31% to 14.57%–8.03% and 17.34%, respectively. The tar removal efficiency varies in the 70%–90% range. When the zeolite was replaced with prepared Ni-based catalysts and hot gas cleaning (HGC) operated at 250 °C, H₂ contents were significantly increased from 6.63% to 12.24% resulting in decreasing the hydrocarbon (tar), and methane content. This implied that NiO could promote the water-gas shift reaction and CH₄ reforming reaction. Under other conditions in which the hot gas temperature was 400 °C, deactivated effects on prepared Ni-based catalyst were observed for inhibiting syngas and tar reduction in the HGC system. The prepared Ni-based catalyst worked at 250 °C demonstrate higher stability, catalyst activity, and less coke decomposition in dry reforming. In summary, the optimum catalytic performance in syngas production and tar elimination was achieved when the catalytic temperature was 250 °C in the presence of prepared Ni-based catalysts, producing 5.92 MJ/kg of lower heating value (LHV) and 73.9% tar removal efficiency.     

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.     

Improved yield parameters in catalytic steam gasification of forestry residue; optimizing biomass feed rate and catalyst type

The catalytic gasification (900 °C) of forestry industry residue (Eucalyptus saligna) was laboratory-studied. Biomass feed rate and type and amount of catalyst were assayed for their effect on the gasified product composition and the overall energy yield of the gasification reaction. The use of a calcined dolomite catalyst resulted in a combustible gas mixture of adequate calorific power (10.65 MJ m^?3) for use as fuel, but neither the product gas composition nor the energy yield varied significantly with widely different amounts of the catalyst (2 g and 20 g). The use of NiO-loaded calcined dolomite catalysts did not affect the product gas composition significantly but led to a 30% increase in the total product gas volume and to a reduction in the rate of tar and char formation. The catalyst loaded with the smallest amount of NiO studied (0.4 wt%. Ni/Dol) led to the highest energy yield (21.50 MJ kg^?1 on a dry-wood basis) based on the use of the gasified product as fuel. The gasified product was found to have an adequate H₂/CO molar ratio and H₂ content for use as synthesis gas source and partial source of H₂.     

Hydrogen production by methane decomposition using bimetallic Ni–Fe catalysts

The catalytic methane decomposition is the leading method for CO_x-free hydrogen and carbon nanomaterial production. In the present study, calcium-silicate based bimetallic Ni–Fe catalysts have been prepared and used to decompose the methane content of the ‘product gas’ obtained in the biomass gasification process for increasing total hydrogen production. Al₂O₃ was used as secondary support on calcium silicate based support material where Ni or Ni–Fe were doped by co-impregnation technique. The activity of catalysts was examined for diluted 6% methane-nitrogen mixture in a tubular reactor at different temperatures between 600 °C and 800 °C under atmospheric pressure, and data were collected using a quadrupole mass spectrometer. Catalysts were characterized by XRD, SEM/EDS, TEM, XPS, ICP-MS, BET, TPR, and TGA techniques. The relation between structural and textural properties of catalysts and their catalytic activity has been investigated. Even though the crystal structure of catalysts had a significant effect on the activity, a direct relation between the BET surface area and the activity was not observed. The methane conversion increased by increasing temperature up to 700 °C. The highest methane conversion has been obtained as 69% at 700 °C with F3 catalyst which has the highest Fe addition, and the addition of Fe improved the stability of catalysts. Moreover, carbon nanotubes with different diameter were formed during methane decomposition reaction, and the addition of Fe increased the formation tendency.     

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.     

Distributed gasification and power generation from solid wastes

A small-scale gasification system for solid wastes has been developed and tested. In this innovative system, known as the STAR-MEET system, a fixed-bed pyrolyzer combined with a high temperature steam/air reformer is employed. From the experimental results using wood chips and polyolefin sheets as feedstocks, it has been demonstrated that injection of high temperature steam/air mixture into the pyrolysis gas can effectively decomposes tar components in the pyrolysis gas into CO and H₂, resulting in an almost tar-free, clean product gas. A 900 °C class compact metallic heat exchanger has been successfully developed, which serves as the high temperature steam/air generator for the STAR-MEET system. Finally, power generation experiments using a complete STAR-MEET plant have been successfully carried out. These results demonstrate small-scale gasification and power generation system using solid wastes is quite feasible.     

Hydrogen production by gasification of Kenaf under subcritical liquid‒vapor phase conditions

In this study, Kenaf biomass was gasified under subcritical liquid-vapor conditions and effect of initial water amount on gas composition and hydrogen production was evaluated at different temperatures. Gasification was carried out in a batch type reactor, with various initial water volumes (0, 12, 25, 50, 75 mL), at different temperatures (250, 275, 300, 325 °C) and with different catalysts (Ru/C, Pt/C, Na₂CO₃, Fe₂O₃, CaO, CaCO₃ and RuCl₃). The results revealed that the gasification efficiency and hydrogen selectivity are dramatically varied with initial water percentage that was fed to the reactor. The gaseous products obtained from hydrothermal gasification of kenaf were mainly H₂, CO₂, and in lower but varying amounts, CH₄ and C₂H₄. Water soluble RuCl₃ was found to be more effective than water insoluble Ru/C catalyst on biomass gasification. RuCl₃ catalyst has a high catalytic activity for kenaf gasification with greater H₂ selectivity. Maximum total gas (462.5 mL) and H₂ mole fraction in the gaseous product (44.5%) were obtained at 250 °C with RuCl₃ catalyst. The maximum carbon conversion (%) was also obtained with RuCl₃ as 71.3%. Water behaves as both the reaction medium and the second main reactant beside biomass, during the subcritical liquid-vapor phase gasification process.     

Chemical hot gas cleaning concept for the “CHRISGAS” process

The aim of the CHRISGAS project was the development of a gasification technique to produce clean hydrogen-rich synthesis gas from biomass. In order to improve the process efficiency, this work presents a gas cleaning concept, which combines chemical hot gas cleaning with hot (1 MPa, 900 °C) and warm (1 MPa, 300 °C) filtration. As the focus is set on the removal of H₂S, HCl and KCl, calculations on chemical gas cleaning for the hot and warm gas filter were done using a thermodynamic process model using SimuSage? (GTT-Technologies). The calculations show that Ca-based and Fe-based sorbents are not suitable H₂S sorbents under the conditions of the hot gas filter. For Cu-based sorbents, H₂S concentration below 100 cm³ m^?3 is achievable, if the temperature is reduced below 810 °C. Additional calculations of KCl sorption on alumosilicates under the conditions of the hot gas filter show that the alkali concentration in gasifier-derived gases can be limited to 100 mm³ m^?3. Thus, the condensation temperature of KCl can be decreased down to 580 °C. The results of HCl sorption calculations show that Na- and K-based sorbents are only suitable for temperatures below 600 °C. Therefore, the HCl sorption is transferred to the warm gas filter. The KCl sorption results were confirmed by experiments using bauxite, bentonite, kaolinite and naturally occurring zeolite as sorbents.     

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%.     

Experimental study on hydrogen-rich syngas production via gasification of pine cone particles and wood pellets in a fixed bed downdraft gasifier

The main objective of this research is to investigate gasification of pine cones particles and wood pellets in a pilot scale 10 kWth downdraft fixed bed gasifier using air as an oxidizing agent. In this work, it was found that syngas produced by gasification of pinecones particles is rich in environmentally friendly hydrogen and that would be a clean alternative energy carrier for the production of clean energy. In addition, the effect of gasification temperature and equivalence ratio on the composition of syngas and gasification performance for pine cones and wood pellet were analysed comparatively. During the experimental works gasification took place with air, in a temperature range of 701–1046 °C, for various air equivalence ratios (0.14–0.37) and under atmospheric pressure. It is found that H₂ and CO production increased by increasing reactor temperature. Another finding is that the mean cold gas efficiency was 65% for pinecone particles and 80% for wood pellet gasification.     

Catalytic steam co-gasification of biomass and coal in a dual loop gasification system with olivine catalysts

A dual loop gasification system (DLG) has been previously proposed to facilitate tar destruction and H₂-rich gas production in steam gasification of biomass. To sustain the process auto-thermal, however, additional fuel with higher carbon content has to be supplied. Co-gasification of biomass in conjunction with coal is a preferred option. Herein, the heat balance of the steam co-gasification of pine sawdust and Shenmu bituminous coal in the DLG has been analyzed to verify the feasibility of the process with the help of Aspen Plus. Upon which, the co-gasification experiments in the DLG have been investigated with olivine as both solid heat carriers and in-situ tar destruction catalysts. The simulation results show that the self-heating of the DLG in the co-gasification is achieved at the coal blending ratio of 28%, gasification circulation ratio of 19 and reforming circulation ratio of 20 when the gasifier temperature 800 °C, reforming temperature 850 °C, combustor temperature 920 °C and S/C 1.1. The co-gasification experiments indicate that the tar is efficiently destructed in the DLG at the optimized reformer temperature and with olivine catalysts.     

Catalytic poppy seed gasification by lanthanum-doped cobalt supported on sepiolite

In this study, sepiolite as support material, was firstly used to synthesize a series of Co/xLa-SEP catalysts. Besides, a newly proposed biomass, poppy seed, was utilized in gasification for assessment of catalyst activity under various La loadings (0–10 wt% with a 2 wt% increment for each) and temperatures (550, 650, 750, 850 °C). The non-catalytic gasification resulted in the highest H₂ concentration of 3.89 mol/kg poppy seed at 850 °C, whereas, the catalyst with 6 wt% La loading showed superior catalytic performance even at the much lower temperature of 650 °C, yielding 4.75 mol H₂/kg poppy seed. Based on the results, char formation was almost utterly hindered in presence of 10 wt% La laoding at 850 °C, whereas a significant reduction of tar to 3.83 wt% was attained in corporation of 4 wt% La at 750 °C. The prepared catalysts were characterized by X-Ray Fluorescence (XRF), X-Ray Diffraction (XRD), Thermogravimetric Analysis (TGA), Fourier Transform Infrared Spectroscopy (FT-IR), Brunauer-Emmett-Teller (BET) and Scanning Electron Microscopy (SEM). SEM images and BET data presented that the Co/6La-SEP catalyst exhibited smallest particle size and the highest surface area (251.05 m²/g).     

Synthesis and evaluation of biochar-derived catalysts for removal of toluene (model tar) from biomass-generated producer gas

Challenges in removal of contaminants, especially tars, from biomass-generated producer gas continue to hinder commercialization efforts in biomass gasification. The objectives of this study were to synthesize catalysts made from biochar, a byproduct of biomass gasification and to evaluate their performance for tar removal. The three catalysts selected for this study were original biochar, activated carbon, and acidic surface activated carbon derived from biochar. Experiments were carried out in a fixed bed tubular catalytic reactor at temperatures of 700 and 800 °C using toluene as a model tar compound to measure effectiveness of the catalysts to remove tar. Steam was supplied to promote reforming reactions of tar. Results showed that all three catalysts were effective in toluene removal with removal efficiency of 69–92%. Activated carbon catalysts resulted in higher toluene removal because of their higher surface area (∼900 m²/g compared to less than 10 m²/g of biochar), larger pore diameter (19 A° compared to 15.5 A° of biochar) and larger pore volume (0.44 cc/g compared to 0.085 cc/g of biochar). An increase in reactor temperature from 700 to 800 °C resulted in 3–10% increase in toluene removal efficiency. Activated carbons had higher toluene removal efficiency compared to biochar catalysts.     

Hydrogen gas yield and trace pollutant emission evaluation in automotive shredder residue (ASR) gasification using prepared oyster shell catalyst

This work examines the hydrogen gas yield and trace pollutants partitioning in automobile shredder residue (ASR) catalytic gasification by fixed bed and fluidized bed gasifier with controlling at equilibrium ratio (ER) 0.2, temperature 900 °C, and 5%–15% prepared catalyst addition. Oyster shell (OS) is a valuable resource due to its higher calcium content that it could prepare as a catalyst for enhancing the hydrogen production in ASR gasification. In the case of the fixed bed gasifier experiments, the highest lower heating value (LHV) and syngas production were found at 900 °C and 10% OS catalyst addition. The maximum H₂ and CO composition were 6.57% and 5.97%, respectively. The LHV of syngas was approximately 4.43 MJ/Nm³. The fluidized bed gasifier could provide a good ASR decomposition and heat transfer behavior. The syngas yield results indicated the maximum H₂ and CO composition were 12.12% and 10.59%, respectively. It was obviously showed that the syngas production and energy conversion efficiency were enhanced by applying fluidized bed gasifier. The maximum produced gas LHV was 10.77 MJ/Nm³ as well as the cold gas efficiency (CGE) of produced gas was 71.62%. On the other hand, the volatile sulfur and chlorine speciation formed in ASR gasification were mainly partitioned in the solid and/or liquid phase. It implied that tested OS catalysts could inhibit the volatile sulfur and chlorine speciation emission in the produced gas as well as enhance the produced gas quality. In summary, this research could provide basic insight into enhanced syngas production and quality in ASR catalytic gasification using the prepared OS catalyst.     

Parametric gasification process of sugarcane bagasse for syngas production

This research focuses on parametric influence on product distribution and syngas production from conventional gasification. Three experimental parameters at three different levels of temperature (700, 800 and 900 °C), sugarcane bagasse loading (2, 3 and 4 g) and residence time (10, 20 and 30 min) were studied using horizontal axis tubular furnace. Response Surface Methodology supported by central composite design was adopted in order to investigate parameters impact on product distribution (i.e., gas, tar and char) and gaseous products (i.e., H₂, CO, CO₂ and CH₄). The highest H₂ fraction obtained was 42.88 mol% (36.91 g-H₂ kg-biomass⁻¹) at 3 g of sugarcane bagasse loading, 900 °C and 30 min reaction time. The temperature was identified as the most influential parameter followed by reaction time for H₂ production and diminishing the bio-tar and char yields. An increase in sugarcane bagasse loading, on other hand, favored the production of bio-tar, CO₂ and CH₄ production. The statistical analysis verified temperature as most significant (p-value 0.0008) amongst the parameters investigated for sugarcane bagasse biomass gasification.