Low-temperature gasification of a woody biomass under a nickel-loaded brown coal char

Catalytic gasification of a woody biomass, Japanese cypress, was investigated under a prepared nickel-loaded brown coal (LY-Ni) char in a two-stage fixed-bed reactor. The nickel-loaded brown coal was prepared by ion-exchange method with a nickel loading rate of 8.3 wt.%. Nickel species dispersed well in the brown coal, and the LY-Ni char via devolatilization at 600 °C showed a great porous property with a specific surface area of 382 m² g^− 1.The LY-Ni char was confirmed to be quite active for the Japanese cypress volatiles gasification at a relatively low-temperature range from 450 to 650 °C. For example, at 550 °C, 16.6 times hydrogen gas and 6.3 times total gases were yielded from the catalytic steam gasification of Japanese cypress volatiles under the LY-Ni char, compared with the case of non-catalyst. The biomass tar decomposition showed a dependence on catalyst temperatures. When the catalyst temperature was higher than 500 °C, Japanese cypress tar converted much efficiently, high gas yields and high carbon balances were obtained.     

Volatilisation and catalytic effects of alkali and alkaline earth metallic species during the pyrolysis and gasification of Victorian brown coal. Part IV. Catalytic effects of NaCl and ion-exchangeable Na in coal on char reactivity

The purpose of this study is to investigate the catalytic effects of Na as NaCl or as sodium carboxylates (-COONa) in Victorian brown coal on the char reactivity. A Na-exchanged coal and a set of NaCl-loaded coal samples prepared from a Loy Yang brown coal were pyrolysed in a fluidised-bed/fixed-bed reactor and in a thermogravimetric analyser (TGA). The reactivities of the chars were measured in air at 400 °C using the TGA. The experimental data indicate that the Na in coal as NaCl and as sodium carboxylates (-COONa) had very different catalytic effects on the char reactivity. It is the chemical form and dispersion of Na in char, not in coal, that govern the catalytic effects of Na. For the Na-form (Na-exchanged) coal, the char reactivity increased with increasing pyrolysis temperature from 500 to 700 °C and then decreased with pyrolysis temperature from 700 to 900 °C. The increase in reactivity with pyrolysis temperature (500-700 °C) is mainly due to the changes in the relative distribution of Na in the char matrix and on the pore surface. For the NaCl-loaded coals, when Cl was released during pyrolysis or gasification, the Na originally present in coal as NaCl showed good catalytic effects for the char gasification. Otherwise, Cl would combine with Na in the char to form NaCl during gasification, preventing Na from becoming an active catalyst. Controlling the pyrolysis conditions to favour the release of Cl can be a promising way to transform NaCl in coal into an active catalyst for char gasification.     

Effects of Chinese dolomites on tar cracking in gasification of birch

To minimize tar in the producer gas from birch gasification at 700, 750 and 800 °C, four Chinese dolomites (Zhenjiang, Nanjing, Shanxi, Anhui) and a Swedish dolomite (Sala) used as reference were studied in a laboratory-scale atmospheric fluidized bed gasifier. The gasifier was equipped with a downstream fixed catalyst bed. The results imply that all dolomites but Anhui dolomite effectively decompose tar into gases. Anhui dolomite showed a low catalytic capacity to crack tar produced at 700 and 800 °C. The influence of various ratios of steam to biomass on tar content in the producer gas after passing over dolomite was studied. The tar cracking efficiency of the dolomites did not improve significantly with the ratio of steam to biomass in the region 0.11-0.52.     

Experimental comparison of biomass chars with other catalysts for tar reduction

In this paper the potential of using biomass char as a catalyst for tar reduction is discussed. Biomass char is compared with other known catalysts used for tar conversion. Model tar compounds, phenol and naphthalene, were used to test char and other catalysts. Tests were carried out in a fixed bed tubular reactor at a temperature range of 700–900 °C under atmospheric pressure and a gas residence time in the empty catalyst bed of 0.3 s. Biomass chars are compared with calcined dolomite, olivine, used fluid catalytic cracking (FCC) catalyst, biomass ash and commercial nickel catalyst. The conversion of naphthalene and phenol over these catalysts was carried out in the atmosphere of CO₂ and steam. At 900 °C, the conversion of phenol was dominated by thermal cracking whereas naphthalene conversion was dominated by catalytic conversion. Biomass chars gave the highest naphthalene conversion among the low cost catalysts used for tar removal. Further, biomass char is produced continuously during the gasification process, while the other catalysts undergo deactivation. A simple first order kinetic model is used to describe the naphthalene conversion with biomass char.     

Comprehensive study of the influence of total pressure on products yields in fluidized bed gasification of wood sawdust

Wood sawdust gasification experiments were performed in a steam fluidized bed at 800 °C between 2 and 10 bar. An evolution of gas yields with time was measured during the tests, and especially an increase of hydrogen and carbon dioxide yields. This test duration effect was ascribed to char build-up in the bed. As tests proceed, the contribution of char steam gasification to gas yield increases, and the catalytic effect of char on hydrocarbons and tar conversion and on water-gas shift reaction is enhanced.As total pressure increases from 2 to 10 bar, hydrogen, carbon dioxide and methane yields increase by 16%, 53% and 38% respectively, whereas carbon monoxide yield decreases by 33%. The changes in gaseous yields with pressure can be partly explained by the influence of pressure on gas phase reactions (acceleration of water-gas shift kinetics and change in hydrocarbon reactions). The increase of methane yield with pressure is rather suggested to be linked to a change in secondary pyrolysis reactions scheme under high pressure.     

Steam gasification of coal char catalyzed by K2CO3 for enhanced production of hydrogen without formation of methane

Steam gasification of coal char catalyzed by potassium carbonate was investigated on a laboratory fixed-bed reactor to examine the catalytic effects not only on the reaction rate but also on the reaction selectivity, and non-catalytic gasification of coal char was performed by way of contrast. It was observed that the catalytic gasification of coal char with steam occurred significantly in a temperature range of 700-750 °C, producing a hydrogen-rich gas with slight formation of carbon monoxide and virtually no formation of methane. An oxygen transfer and intermediate hybrid mechanism of the catalytic char gasification with steam is proposed for understanding of the experimental data regarding both the kinetic behaviors and reaction selectivity. The study has highlighted the advantages of the catalytic gasification of coal char over the conventional coal gasification with respect to the reaction selectivity. The catalytic steam gasification of coal char makes it possible to eliminate or simplify the methane reforming and water-gas shift processes in the traditional gas-to-hydrogen purification system.     

Fate of the chlorine and fluorine in a sub-bituminous coal during pyrolysis and gasification

The fate of the chlorine and fluorine present in a sub-bituminous coal from Indonesia during pyrolysis and gasification has been studied with fixed and entrained bed reactors. The rate profile for HCl evolved in the temperature programmed pyrolysis exhibits the main and shoulder peaks at 480 and 600 °C, respectively. Model experiments and subsequent Cl 2p XPS measurements show that HCl reacts with metal impurities and carbon active sites at 500 °C to be retained as inorganic and organic chlorine forms, from which HCl evolves again at elevated temperatures. It is suggested that the HCl observed in the coal pyrolysis may originate from the above-mentioned chlorine functionalities formed by secondary reactions involving the nascent char. In the CO₂ gasification of the 900 °C char at 1000 °C and 2.5 MPa, any measurable amounts of HCl and HF could not be detected even at a high conversion of 75 wt% (daf), suggesting the accumulation of these halogens in the residual char. When the coal is injected into an O₂-blown, entrained bed gasifier at 1200-1400 °C under 2.6 MPa, the partial oxidation proceeds to a larger extent at a higher O₂/coal ratio, whereas the chlorine and fluorine are enriched in the remaining char, and the extent of the enrichment at the latter stage of gasification is larger with the fluorine. The XPS measurements of the chars reveal the presence of the broad F 1 s peak, which can cover a wide range of binding energies attributable to inorganic and organic fluorine. The halogen enrichment during gasification is discussed in terms of secondary reactions of HCl and HF with char.     

Tar destruction and coke formation during rapid pyrolysis and gasification of biomass in a drop-tube furnace

This paper describes tar destruction and coke (or soot) formation of biomass in three different conversion processes: pyrolysis (in a pure nitrogen stream), steam gasification (in a mixture stream of steam and nitrogen), and partial oxidation (in a mixture stream of oxygen and nitrogen), over a wide temperature range from 600 to 1400 °C. A woody waste, hinoki cypress sawdust (HCS), was used as a feedstock, and an entrained drop-tube furnace (DTF) was applied to all experimental tests. It is found that raising the temperature remarkably decreases tar evolution. Steam and oxygen also have a positive effect on tar destruction. Benzene and toluene are the most difficult condensable tar species to destroy. The achievement of their complete destruction in the product gas requires extremely high temperatures above 1200 °C, regardless of the gasifying agents. The coke deposits from 900 °C and reaches a maximum formation at 1000 or 1100 °C. The results obtained in this study suggest that competition occurs between the secondary decomposition of hydrocarbon species and gasification reactions of the produced char and/or coke with gasifying agents in the temperature range of 900-1100 °C.     

Mechanisms and kinetics of homogeneous secondary reactions of tar from continuous pyrolysis of wood chips

The change of mass and composition of biomass tar due to homogeneous secondary reactions was experimentally studied by means of a lab reactor system that allows the spatially separated production and conversion of biomass tar. A tarry pyrolysis gas was continuously produced by pyrolysis of wood chips (fir and spruce, 10-40 mm diameter) under fixed-bed biomass gasification conditions. Homogeneous secondary tar reactions without the external supply of oxidising agents were studied in a tubular flow reactor operated at temperatures from 500 to 1000 °C and with space times below 0.2 s. Extensive chemical analysis of wet chemical tar samples provided quantitative data about the mass and composition of biomass tar during homogeneous conversion. These data were used to study the kinetics of the conversion of gravimetric tar and the formation of PAH compounds, like naphthalene.It is shown that, under the reaction conditions chosen for the experiments, homogeneous secondary tar reactions become important at temperatures higher than 650 °C, which is indicated by the increasing concentrations of the gases CO, CH₄, and H₂ in the pyrolysis gas. The gravimetric tar yield decreases with increasing reactor temperatures during homogeneous tar conversion. The highest conversion reached in the experiments was 88% at a reference temperature of 990 °C and isothermal space time of 0.12 s. Hydrogen is a good indicator for reactions that convert the primary tar into aromatics, especially PAH. Soot appears to be a major product from homogeneous secondary tar reactions.     

Catalytic activities of ion-exchanged nickel and iron in low temperature hydrogasification of raw and modified birch chars

Raw, HNO₃ oxidized and carboxymethylated birch woods loaded with nickel or iron by the ion-exchange method were carbonized at 500 °C in a flow of nitrogen, and the resulting chars were hydrogasified in a thermobalance to examine their reactivities below 700 °C. The amounts of ion-exchanged metals on raw char were too small to give high gasification reactivity. However, oxidized and carboxymethylated woods with increased ion-exchange capacity produced much more reactive chars. Both nickel and iron exhibited larger catalytic activities on carboxymethylated chars than on oxidized chars, because better metal dispersion could be achieved on carboxymethylated wood with its larger cation exchangeability. It was noteworthy that only 1 wt% loading of iron, as well as nickel, on carboxymethylated char was sufficient to attain a gasification of 90 wt% at 700 °C. It was also noted that the catalytic effect, up to 600 °C, of iron on the gasification of oxidized and carboxymethylated chars was larger than that of nickel. This is ascribed to two factors; greater catalytic activity of metallic iron formed during the gasification than that of nickel metal, and low ash level in the chars. Above 600 °C, however, serious loss of activity of the iron was observed in the absence of wood ash. This showed the different influence of wood ash on the catalysis of iron in the low and high temperature regions.     

Impact of torrefaction on syngas production from wood

Torrefaction is a way to treat biomass before transportation or thermochemical conversion. It can be used to increase the energy content of wood or to facilitate grinding. The purpose of this paper was to quantify the impact of such a treatment on the behaviour of wood during gasification by steam at high temperature to produce syngas. The aspects of both gas yields and reaction kinetics were considered.Beechwood was submitted both to light torrefaction and severe torrefaction, using a specially designed crossed fixed bed reactor. The initial wood and the torrefied woods were first characterised, then gasified in a new laboratory high-temperature entrained flow reactor (HT-EFR) at 1400 °C for 2 s in an atmosphere containing 20 vol% steam in N₂. The syngas produced was then analysed. The experiments were modelled using a thermo-dynamical equilibrium approach.It was confirmed that torrefaction decreased the O/C ratio. The quantity of syngas produced increased with the severity of the torrefaction. The equilibrium approach describes the results satisfactorily.Gasification experiments carried out at a lower temperature - 1200 °C - indicated that the chars from torrefied woods are less reactive towards steam than the char from wood.     

Volatilisation and catalytic effects of alkali and alkaline earth metallic species during the pyrolysis and gasification of Victorian brown coal. Part IX. Effects of volatile-char interactions on char-H2O and char-O2 reactivities

Volatile-char interactions are an important consideration in the design and operation of a gasifier. This study aims to investigate the effects of volatile-char interactions on the in situ char-steam reactivity at 800 °C and the ex-situ char-O₂ reactivity at 400 °C. A Victorian brown coal was gasified in 15% steam at 800 °C in a one-stage novel fluidised-bed/fixed-bed quartz reactor, in which the extent of volatile-char interactions could be controlled. The chars after varying extents of volatile-char interactions and/or varying extents of char conversion in steam were also collected for the measurement of their reactivity with air at 400 °C in a thermogravimetric analyser. Our results show that the char-steam gasification reactions were greatly inhibited by the volatile-char interactions. It is believed that the H radicals generated from the thermal cracking/reforming of volatiles slowed the char gasification in three ways: occupying the char reactive sites, causing the char structure to re-arrange/condense and enhancing the release of catalytic species inherently present in the brown coal. The importance of volatile-char interactions to char-steam reactivity was further confirmed by the char-air reactivity.     

Hydrogen production via gasification of meat and bone meal in two-stage fixed bed reactor system

Gasification of meat and bone meal followed by thermal cracking of tar was carried out at atmospheric pressure using a two-stage fixed bed reaction system in series. The first stage was used for the gasification and the second stage was used for thermal cracking of tar. In this work, the effects of temperature (650-850 °C) of both stages, equivalence ratio (actual O₂ supply/stoichiometric O₂ required for complete combustion) (0.15-0.3) and the second stage packed bed height (40-100 mm) on the product (char, tar and gas) yield and gas (H₂, CO, CO₂, CH₄, C₂H₄, C₂H₆, C₃H₆, C₃H₈) composition were studied. It was observed that the two-stage process increased hydrogen production from 7.3 to 22.3 vol.% (N₂ free basis) and gas yield from 30.8 to 54.6 wt.% compared to single stage. Temperature and equivalence ratio had significant effects on the hydrogen production and product distribution. It was observed that higher gasification (850 °C) and cracking (850 °C) reaction temperatures were favorable for higher gas yield of 52.2 wt.% at packed bed height of 60 mm and equivalence ratio of 0.2. The residence time of tar and product gases was varied by varying the packed bed height of second stage. The tar yield decreased from 18.6 wt.% to 14.2 wt.% and that of gas increased from 50.6 wt.% to 54.6 wt.% by changing the packed bed height of second stage from 40 to 100 mm while the gross heating value (GHV) of the product gas remained almost constant (16.2-16.5 MJ/m³).     

Steam gasification reactivity of char from rapid pyrolysis of bio-oil/char slurry

A slurry of bio-oil and char originating from wood pyrolysis is a promising gasifier feed-stock because of its high energy density. When such a slurry is injected into a high temperature gasifier it undergoes a rapid pyrolysis yielding a char which then reacts with steam. The char produced by pyrolysis of an 80 wt% bio-oil/20 wt% char mixture at heating rates of 100-10,000 °C/s was subjected to steam gasification in a thermogravimetric analyzer. The original wood char from the bio-oil production was also tested. Gasification was conducted with 10-50 mol% steam at temperatures from 800 to 1200 °C. Reactivity of the slurry chars increased with pyrolysis heating rate, but was lower than that of the original chars. Kinetic parameters were established for a power-law rate model of the steam-char reaction, and compared to values from the literature. At temperatures over 1000 °C, the gasification rates appeared to be affected by diffusional resistance.     

The effect of steam on pyrolysis and char reactions behavior during rice straw gasification

Steam gasification of biomass can generate hydrogen-rich, medium heating value gas. We investigated pyrolysis and char reaction behavior during biomass gasification in detail to clarify the effect of steam presence. Rice straw was gasified in a laboratory scale, batch-type gasification reactor. Time-series data for the yields and compositions of gas, tar and char were examined under inert and steam atmosphere at the temperature range of 873-1173 K. Obtained experimental results were categorized into those of pyrolysis stage and char reaction stage. At the pyrolysis stage, low H₂, CO and aromatic tar yields were observed under steam atmosphere while total tar yield increased by steam. This result can be interpreted as the dominant, but incomplete steam reforming reactions of primary tar under steam atmosphere. During the char reaction stage, only H₂ and CO₂ were detected, which were originated from carbonization of char and char gasification with steam (C + H₂O→CO + H₂). It implies the catalytic effect of char on the water-gas shift reaction. Acceleration of char carbonization by steam was implied by faster hydrogen loss from solid residue.     

整体式新型生物质气化催化反应器的实验研究

在现有生物质气化反应器及焦油处理方法的基础上,开发出一种整体式新型生物质气化催化反应器,并对该反应器进行相关的实验研究。实验研究结果表明:当木粉进料速率为6.48 g/min,空燃比RE为0.23,气化温度在500—670℃,这种整体式新型生物质气化催化反应器内有、无催化剂时对木粉气化产生的燃气中焦油的含量以及气体组分有明显影响;当采用钴与氧化钴的质量分数为20%,氧化钙的质量分数为80%的钴基催化剂作为焦油裂解催化剂,裂解温度为800℃,标态下体积空时为1.8 s的情况下,燃气中夹带的焦油可完全被催化裂解,同时燃气中的气体成分氢体积分数可从无催化剂时的15%提高到有催化剂时的35%,净提高20%。同时也对使用前后的钴基催化剂进行了XRD表征分析,发现氧化钙在生物质气化过程中具有一定的CO2捕集能力。     

Pyrolysis behavior of vitrinite and inertinite from Chinese Pingshuo coal by TG-MS and in a fixed bed reactor

The pyrolysis behaviors of vitrinite and inertinite from Chinese Pingshuo coal were investigated by using the thermogravimetry coupled with mass spectrometry (TG-MS) and in a fixed bed reactor, respectively. The results showed that inertinite has lower pyrolysis reactivity, lower tar and gas yields, but higher water yield than vitrinite. At 650 °C, the tar and gas yield of vitrinite is 22.4% and 14.4%, respectively, obviously higher than 13.4% and 10.2% of inertinite. The TG-MS analysis also showed much difference of vitrinite and inertinite in gas evolution profile. The ultimate and XRD analyses of chars indicated that the difference in element composition of vitrinite char and inertinite char decreases with the increase of temperature, and have similar element composition and structure characteristic at 650 °C. The total sulfur removal of both vitrinite and inertinite increases with the pyrolysis temperature, and reaches to 60% at 650 °C, but the organic sulfur in inertinite seems more stable than that in vitrinite.     

Nickel catalysed steam gasification of chars obtained from coal-alkali reaction at 600 °C

Studies on the steam gasification of washed residual chars (obtained from coal-alkali reaction at 600 °C) were carried out at 500 °C and 100 kPa pressure in a fixed bed glass reactor with or without nickel (as nickel nitrate) as catalyst. The results when compared with the corresponding data on coal, revealed that under similar reaction conditions, the coals yielded more gas with higher H₂ and CO contents than their corresponding chars. It was concluded that presence of functional groups, especially oxygen containing is a requirement for nickel catalysed steam gasification of coals/lignites. The recovery of nickel achieved was about 80%.     

Pyrolysis of wood at high temperature: The influence of experimental parameters on gaseous products

The pyrolysis of wood was carried out in an Entrained Flow Reactor at high temperature (650 to 950 °C) and under rapid heating conditions (> 10³ K s^− 1). The influence of the diameter and initial moisture of the particle, reactor temperature, residence time and the nature of the gaseous atmosphere on the composition of the gaseous products has been characterised. Particle size, between 80-125 and 160-200 μm, did not show any impact. Pyrolysis and tar cracking essentially happen in very short time period: less than 0.6 s; the products yields are only slightly modified after 0.6 s in the short residence times (several seconds) of our experiments. Higher temperatures improve hydrogen yield in the gaseous product while CO yield decreases. Under nitrogen atmosphere, after 2 s at 950 °C, 76% (daf) of the mass of wood is recovered as gases: CO, CO₂, H₂, CH₄, C₂H₂, C₂H₄ and H₂O. Tests performed under steam partial pressure showed that hydrogen production is slightly enhanced.     

Effect of bed depth on characterisation of slow pyrolysis products

The trend towards separation of waste for material recovery could assist with the implementation of waste pyrolysis and gasification processes. Following the previous work on slow pyrolysis of segregated waste materials, this study investigated the effect of bed depth on the yields and properties of pyrolysis products in a fixed bed pyrolyser. The results showed that the bed depth had a strong influence on the properties of pyrolysis products but a small effect on the yield of products. Differences in the liquid yield between the two cases of bed depth (17-57 vol% of the reactor) were observed at temperatures above 500 °C while the difference in the char yield was negligible. The aqueous fraction was 5-15% higher for the bed depth of 57 vol% than for the bed depth of 17 vol%. Increase in the bed depth increased the H/C ratio by a factor of 2-6 in the char product and the CO/CO₂ ratio by a factor of 1.74 in the gas product but slightly decreased in the H/C ratio in the liquid product.