Co–gasification of coal/biomass blends in 50 kWe circulating fluidized bed gasifier

This paper reports gasification of coal/biomass blends in a pilot scale (50 kWe) air-blown circulating fluidized bed gasifier. Yardsticks for gasification performance are net yield, LHV and composition and tar content of producer gas, cold gas efficiency (CGE) and carbon conversion efficiency (CCE). Net LHV decreased with increasing equivalence ratio (ER) whereas CCE and CGE increased. Max gas yield (1.91 Nm³/kg) and least tar yield (5.61 g/kg of dry fuel) was obtained for coal biomass composition of 60:40 wt% at 800 °C. Catalytic effect of alkali and alkaline earth metals in biomass enhanced char and tar conversion for coal/biomass blend of 60:40 wt% at ER = 0.29, with CGE and CCE of 44% and 84%, respectively. Gasification of 60:40 wt% coal/biomass blend with dolomite (10 wt%, in-bed) gave higher gas yield (2.11 Nm³/kg) and H₂ content (12.63 vol%) of producer gas with reduced tar content (4.3 g/kg dry fuel).     

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.     

From coal towards renewables: Catalytic/synergistic effects during steam co-gasification of switchgrass and coal in a pilot-scale bubbling fluidized bed

Recent environmental sharp curbs on fossil fuel energy systems such as coal power plants due to their greenhouse gas emissions have compelled industries to include renewable fuels. Biomass/coal co-gasification could provide a transition from energy production based on fossil fuels to renewables. A low-ash coal and switchgrass rich in potassium were selected on the basis of previous thermogravimetric studies to steam co-gasify 50:50 wt% coal:switchgrass mixtures in a pilot scale bubbling fluidized bed reactor with silica sand as the bed material at ∼800 and 860 °C and 1 atm. With the switchgrass added to coal, the hydrogen and cold gas efficiencies, gas yield and HHV of the product gas were enhanced remarkably relative to single-fuel gasification. The product gas tar yield also decreased considerably due to decomposition of tar catalyzed by switchgrass alkali and alkaline earth metals. Switchgrass ash therefore can act as inexpensive natural catalysts for steam gasification and assist in operating at lower temperatures without being penalized by an increase in product tar yield. An equilibrium model over-predicted hydrogen and under-predicted methane concentrations. However, an empirically kinetically-modified model was able to predict the product gas compositions accurately.     

Pyrolysis waste char supported metallic catalyst for syngas production during catalytic reforming of benzene

Waste rice husk char supported Fe and Ni were synthesized to prepare the monometallic and bimetallic catalysts for removing the tar model compound benzene in a laboratory dual-stage reactor. The prepared catalysts were examined by microstructure and textural characterization to analyse catalytic performance and stability. The molar proportions of CO, H₂, CO₂ and CH₄ in the generated gas and the influence of residence time (τ) and the steam-to-carbon ratio (S/C) on the catalytic reaction were investigated. The results show that the rice husk char-based catalysts showed excellent catalytic activity for syngas production and benzene conversion. Under optimized conditions, the benzene conversion can reach 95.2%, and the mol% of syngas in the generated gas is greater than 93.0%, of which 91.0% is H₂. The experimental results show that the influence of residence time on catalytic performance is greater than that of the steam-to-carbon ratio, and that excessive τ or S/C values will have no more positive effect on the performance of the catalyst. The stable active sites on the catalyst surface can guarantee the catalytic activity in the reaction. Ultimately, rice husk char-based catalysts can be used to remove tar and produce syngas.     

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.     

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.     

Study on Al<Subscript>2</Subscript>O<Subscript>3</Subscript> extraction from activated coal gangue under different calcination atmospheres

Coal gangue was calcinated under air, nitrogen, carbon dioxide, air–hydrogen, and hydrogen atmospheres. The effects of different calcination temperatures and atmospheres on the mineral composition of activated coal gangue were investigated by X-ray diffraction. Moreover, the acid leaching kinetics of aluminum oxide from coal gangue was investigated with sulfuric acid. It showed that the air atmosphere promoted kaolinite decomposition during coal gangue calcination. The hydrogen atmosphere promoted the activation and decomposition of kaolinite at reaction temperatures exceeding 650°C. The carbon dioxide atmosphere eliminated the influence of residual carbon on coal gangue. When the ratio of acid/coal gangue was 1.5 and reaction temperature was 650°C, the sulfuric acid leaching rate under air, air-hydrogen, carbon dioxide, hydrogen and nitrogen atmospheres were 93.66%, 90.90%, 84.06%, 81.91% and 77.54% respectively. The acid leaching reaction process conformed to unreacted shrinking core model of particle unchanged, and was controlled by the interfacial chemical reaction. The reaction kinetic equation for the leaching process was 1-(1-x)1/3=kt with an apparent activation energy of 48.97 kJ/mol.     

Experimental study on the coal tar hydrocracking process over different catalysts

In the paper, the results of the study on a laboratory process of hydrocracking of coal tar are presented. High-temperature coal tar was hydrocracked in an autoclave reactor, at 400–413 °C and 7,3–9,6 MPa over 5 different, hydrocracking catalysts to study the yields and characteristics of the products. Liquid products were obtained with a yield of 88–92 wt.% and gas products with a yield of 12–8 wt.%. After dehydration by azeotropic distillation, liquid products were separated on the oil fraction boiling below 360 °C, and pitch fractions boiling above this temperature. In the balance of distillation, it is clear that only the cracking activity of NiW/Al₂O₃ and Y zeolite catalysts is so high that the raw material containing 5 vol.% fraction boiling below 200 °C provides a product comprising approx. 12,5 vol.% of this fraction. The influence of five different catalysts on the yield of 18 poly aromatic hydrocarbons (PAHs) in the hydrocracking products have been investigated by GC/MS. The results indicate that NiW/Al₂O₃ and Y zeolite catalysts have the highest catalytic activity for light aromatic formation (the highest yield of fraction boiling below 200 °C) and aromatic condensed aromatic cracking (PAHs). After the hydrocracking NiW/Al₂O₃ catalyst, the total yields of PAHs decrease 52.7% as that of raw coal tar.     

Tar removal from biomass pyrolysis gas in two-step function of decomposition and adsorption

Tar content in syngas pyrolysis is a serious problem for fuel gas utilization in downstream applications. This paper investigated tar removal, by the two-step function of decomposition and adsorption, from the pyrolysis gas. The temperature of the tar decomposition process was fixed at 800 °C both with and without steam, with air as the reforming agent. Both steam and air had a strong influence on the tar decomposition reaction. The reduction of the gravimetric tar mass was 78% in the case of the thermal cracking, whereas, it was in the range of 77–92% in the case of the steam and air forming. Under conditions of tar decomposition, the gravimetric tar mass reduced, while the yield of the combustible gaseous components in the syngas increased. Synchronously, the amount of light tars increased. This should be eliminated later by fixed-bed adsorption. Three adsorbents (activated carbon, wood chip, and synthetic porous cordierite) were selected to evaluate the adsorption performance of light tars, especially of condensable tar. Activated carbon showed the best adsorption performance among all light tars, in view of the adsorption capacity and breakthrough time. On the other hand, activated carbon decreased the efficiency of the system due to its high adsorption performance with non-condensable tar, which is a combustible substance in syngas. Synthetic porous cordierite showed very low adsorption performance with almost all light tars, whereas, wood chip showed a high adsorption performance with condensable tar and low adsorption performance with non-condensable tar. When compared with other adsorbents, wood chip showed a prominent adsorption selectivity that was suitable for practical use, by minimizing the condensable tar without decreasing the efficiency of the system.     

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.     

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 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.     

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.     

Low temperature reduction of NO by activated carbons impregnated with Fe based catalysts

In the present study, the reduction of NO by two activated carbons without and loaded with Fe based catalysts was studied at 300 °C using a fixed-bed reactor. The activated carbon samples impregnated with and without the catalysts were characterized using TGA, SEM, gas adsorption, ICP-AES, XPS and XRD. The experimental results showed that neither of the raw activated carbons achieved the required denitrification performance. However, compared with coal derived activated carbon (C₀), biomass derived activated carbon (B₀) performed better. The denitrification efficiency improved with the O₂ content in the flue gas, achieved a maximum approximately at 3% O₂, and then decreased with further increase in the O₂ content. The effect of the metals loaded and addition amount of the catalysts was then examined in detail with the biomass derived activated carbon. At the same dosage of catalysts, the biomass derived activated carbon impregnated with K ions was apparently more efficient than it counterpart loaded with Fe ions. A higher addition rate of Fe was required in order to be efficient in NO conversion. Addition of K was further found to significantly improve the NO conversion efficiency of the biomass activated carbon loaded with 3% Fe which otherwise showed a sharp premature decrease in NO conversion efficiency immediately after the flue gas was introduced. Finally the effects contributing to the synergetic effect of Fe and K are discussed.     

生物质焦油裂解催化剂研究进展

对生物质焦油裂解催化剂的研究发展近况进行了阐述，总结了白云石、碱金属催化剂和镍基催化剂三大类催化剂的特点和应用情况，以及展望了焦油裂解技术的发展前景。     

Influence of coal co-firing on the particulate matter formation during pulverized biomass combustion

Biomass is regarded as CO₂-neutral, while the high contents of potassium and chlorine in biomass induce severe particulate matter emission, ash deposition, and corrosion in combustion facilities. Co-firing biomass with coal in pulverized-combustion (PC) furnaces is able to solve these problems, as well as achieve a much higher generating efficiency than grate furnaces. In this work, the particulate matter (PM) emission from biomass co-firing with coal was studied in an entrained flow reactor at a temperature of 1623 K simulating PC furnace condition. PMs were sampled through a 13-stage impactor, and their morphology and elemental composition were characterized by scanning electron microscopy and electron dispersive X-ray spectroscopy. SO₂ emissions were measured to interpret the possibility of potassium sulfation during co-firing. Results show that PMs from the separated combustion of both biomass and coal present a bimodal particle size distribution (PSD). The concentration and size of fine-mode submicron particles (PM_1.0) from biomass combustion are much higher than those from coal combustion because of the high potassium content in biomass. For the co-firing cases, with the coal ratio increasing from 0% to 50%, the PM_1.0 yield is reduced by more than half and the PM_1.0 size becomes smaller, in contrast, the concentration of coarse-mode particles with the size of 1.0–10 μm (PM_1.0-10) increases. The measured PM_1.0 yields of co-firing are lower than the theoretically weight-averaged ones, which proves that during the biomass and coal co-firing in PC furnaces, the vaporized potassium from biomass can be efficiently captured by these silicon-aluminate oxides in coal ash. In the studied range of coal co-firing ratio (≤50 wt.%), the chlorides and sulfates of alkali metals from biomass burning are the dominating components in PM_1.0, and a certain amount of silicon is observed in PM_0.1-1. The analysis of chemical composition in PM_1.0, together with that of SO₂ emission, indicates a marginal sulfation of alkali metal chloride occurring at high temperatures in PC furnaces.     

Microwave-assisted metal-catalyzed pyrolysis of low-rank coal: Promising option towards obtaining high-quality products

Microwave-assisted catalytic pyrolysis is considered to be a promising technology for coal-staged conversion due to its high efficiency and selectivity. This work was undertaken to investigate the pyrolysis behavior and products quality of microwave-assisted pyrolysis of low rank coal catalyzed by metallic catalysts (K, Ca and Fe) with both dielectric response and catalytic effect via a microwave tube furnace. The mechanism of metallic catalysts on catalytic cracking tar under microwave radiation was also investigated. The dielectric properties and physicochemical structure of coal chars were characterized by a vector network analyzer, XRD, FT-IR, SEM, EDS, and Raman. The chemical structure characteristics of generated tars were determined by FT-IR and GC-MS. Results manifested that microwave interacted preferentially with metal catalysts by polarization and conductivity loss could efficiently induce the occurrence of catalytic pyrolysis reactions to generate high yield syngas (CO + H₂). Specifically, the dielectric loss factor of resultant chars was considerably improved with the introduction of metallic catalysts especial for Ca and Fe. Furthermore, it is found that metal catalysts dramatically enriched the amorphous carbon structure in produced chars whereas in favour of suppressing the trend of carbon graphitization. Additionally, the transformation of larger polycyclic aromatic compounds into lighter tar species was catalytically accelerated, resulting in the large proportion of single-ring aromatics in tar under the synergistic effect between microwave and metal catalysts.     

Release and transformation characteristics of Na/Ca/S compounds of Zhundong coal during combustion/CO2 gasification

Zhundong (ZD) coal from northwest China is a high quality steam coal with reserves of more than 390 billion tons. However, the utilization of ZD coal is limited due to the high content of alkali and alkaline earth metals. This study aimed at revealing the release and transformation mechanism of Na/Ca/S compounds during combustion/gasification of ZD coal. The results demonstrate that Na was primarily influenced by temperature, mostly releases at 600–800 °C. The transformation of Ca compounds was affected by both temperature and atmosphere. The high temperature of the combustion process could accelerate the decomposition of CaCO₃ and CaSO₄, and the high content of CO₂ during gasification prolonged the decomposition of CaCO₃. The transformation of S was primarily influenced by atmosphere. SO₂ could react with CaO and form CaSO₄ during the combustion process. While S compounds were mainly released as S (g) and H₂S (g) during gasification process. There was a significant interaction among Na/Ca/S compounds during combustion, original CaSO₄ in coal could adsorb Na compounds with SO₂ at 600–800 °C and then reacted with aluminosilicates, by this reaction, Na could be fixed above 1000 °C.     

Catalytic reforming of biomass primary tar from pyrolysis over waste steel slag based catalysts

Steel slag (SS) contains high amounts of metal oxides and could be applied as the catalyst or support material for the reforming of biomass derived tar. In this research, steel slag supported nickel catalysts were prepared by impregnation of a small amount of nickel (0–10 wt%) and calcination at 900 °C, and then tested for the catalytic reforming of biomass primary tar from pine sawdust pyrolysis. The steel slag after calcination was mainly composed of Fe₂O₃ and MgFe₂O₄, and granular NiO particles was formed and highly dispersed on the surface of nickel loaded steel slag which lead to a porous structure of the catalysts. The steel slag showed good activity on converting biomass primary tar into syngas, and its performance can be further enhanced by the loading of nickel. The yield of H₂ increased significantly with the increase of nickel loading amount, while excessive nickel loading resulted in the decrease in CO and CH₄ yields and significant increase in CO₂ yield. The presence of steam contributed to enhancing the tar steam reforming as well as reactions between steam and produced gases, while decrease the contact probability between the reactants and the active sites of catalysts, leading to a little decrease in tar conversion efficiency but significant increase in syngas yield. The iron and nickel oxides were reduced by the syngas (CO and H₂) from the biomass pyrolysis, and stable and porous structure was formed on the surface of the nickel loaded catalysts during tar reforming.     

Investigation on the thermal behavior characteristics and products composition of four pulverized coals: Its potential applications in coal cleaning

Although the thermochemical conversion of coal has dominated the research concerning the primary chemical production in the coal chemical industry utilization field, obtaining higher tar yield and lighter tar quality remain as challenges. The pyrolysis and its product distribution were studied using a thermogravimetric analyzer and a fixed bed reactor. A gas chromatograph (GC) and a gas chromatograph−mass spectrometer (GC-MS) were employed to test the properties and composition of the pyrolytic products. Here, we demonstrated that the tar yield only fluctuates when the carbon content is approximately 80%. The ratios of aliphatic hydrogen to all the functional groups (Ib₁) are the largest in HM2 coal, while the change of the ratios of aromatic hydrogen to all of the functional groups (Ib₂) is the same as that of the tar yield. With the increase of coalification, the ratio of CH₂ to CH₃ in the aliphatic structure (Ic₁) decreases. The oxygen containing functional groups in YL coal were mostly converted into tar products, but the corresponding functional groups in ZC3 coal decompose to form more water. When the final pyrolysis temperature is below 550 °C, there was a higher yield of gaseous products containing carbon and oxygen than of gaseous products containing hydrogen. With the decrease of the H/C ratio, the relative content of the aliphatic hydrocarbon and phenolic compounds in tar increased, while the benzene series and polycyclic aromatic hydrocarbons decreased.