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.     

生物质气化焦油采样系统的研究进展

介绍了国内外主要生物质气化焦油的采样方法和采样系统,总结了各自的特点,为研究焦油成分提供了参考。     

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.     

Production of a producer gas from woody waste via air gasification using activated carbon and a two-stage gasifier and characterization of tar

Experiments were carried out with a woody waste fraction using a two-stage gasifier consisting of a fluidized bed zone and a tar cracking zone that was filled with activated carbon. In the experiments, the effects of experimental conditions such as the temperature and the equivalence ratio were investigated. In addition, the results of the experiments with virgin activated carbon, without activated carbon, and with spent activated carbon were compared. The producer gases that were obtained in the experiments were analyzed using GCs (FID and TCD) and a GC-MS system. The producer gas obtained with the application of activated carbon at an ER of 0.2 had high H₂ content (16 vol.%, N₂-free), and its lower heating value was above 10 MJ/Nm³. In addition, the total amount of the tar captured by the scrubbers and the electrostatic precipitator was reduced sixfold when activated carbon was applied.     

Characterization of tar content in the syngas produced in a downdraft type fixed bed gasification system from dried sewage sludge

Tar yields in the syngas produced in a pilot-scale downdraft type fixed bed gasification system from dried sewage sludge have been quantified and characterized to identify the effect of equivalence ratio (ER of 0.29-0.36). The increase of ER resulted in higher temperature of oxidation zone because air promoted the combustion reaction. High ER and high temperature also enhanced cracking and combustion of tar. Lower tar mass was observed while increasing ER. The change in tar composition with the change of ER was also observed by using the size exclusion chromatography (SEC). The SEC results showed that heavier molecular tar (in the molecular weight range of 300-500 u) formed whereas lighter molecular tar decreased under the higher ER conditions. Tar removal performances of the gas cleaning system (the venturi scrubbers and the sawdust adsorbers) were also investigated. The tar removal efficiency of the gas cleaning system depended on gasification conditions, tar components and the amount of tar. Tar content in the syngas was reduced to 26-53% and 14-36% (by weight) at the exit of the scrubbers and sawdust adsorbers, respectively. By the action of this gas cleaning system, about 44% of light aromatic hydrocarbon tar was removed while no light PAH tar was detected at the exit of the gas cleaning system.     

Gasification of rice husk in a cyclone gasifier

The experimental results of air gasification of rice husk in the cyclone gasifier were presented at the fuel rate of 20.1 kg/h. With the equivalence ratios varied in the range of 0.21–0.32, the heating value of the producer gas decreases from 6.98 MJ/Nm³ to 3.11 MJ/Nm³ and the cold gas efficiency decreases from 64% to 31%. However, the tar content in the prouder gas decreases with the increase of the equivalence ratio. The rice husk and ash were examined under a scanning electron microscope (SEM) and energy dispersive X-ray (EDX) elemental analysis. The outer surface of the fuel particle which is of scale structure does not change basically during the gasification. The pyrolyzed gas is mainly released from the inner surface of the fuel particle. This work was presented at the 7 ^th China-Korea Workshop on Clean Energy Technology held at Taiyuan, Shanxi, China, June 26–28, 2008.     

The fate of fuel-nitrogen during gasification of biomass in a pressurised fluidised bed gasifier

The distribution of fuel-nitrogen in gases, tar and char from gasification of biomass in a pressurised fluidised bed gasifier was investigated. Four species of biomass: birch, Salix, Miscanthus and Reed canary grass were gasified at 0.4 MPa and 900 °C. Oxygen-enriched nitrogen was used as fluidising agent. As a reference, gasification of Daw Mill coal was also carried out under the same experimental conditions. The experimental results illustrate that both the nature of the original fuels and the chemical structure of the nitrogen in the fuel have influence on the distribution of fuel-nitrogen in gases (NH₃, HCN, NO), tar and char under the employed experimental conditions. The present work also shows that the types of nitrogen heterocyclic compounds (NHCs) in the tar from different kinds of biomass are the same and the major compound is pyridine. However, the distribution of the various NHCs in the tar from the four species of biomass varies: the higher the content of fuel-nitrogen, the higher the concentration of two-ring NHCs in the tar. An effective method for extracting NHCs from the acidic absorption of the product gas was introduced in the present work. The method makes use of solid phase extraction (SPE) by a silica-based C₁₈ tube to extract the NHCs which subsequently were analysed by gas chromatography (GC) with flame ionisation detection (FID). The recovery and reproducibility of the SPE technique for NHCs is discussed.     

Resistance to sulfur poisoning of hot gas cleaning catalysts for the removal of tar from the pyrolysis of cedar wood

In the partial oxidation of tar derived from the pyrolysis of cedar wood, the effect of H₂S addition was investigated over non-catalyst, steam reforming Ni catalyst, and Rh/CeO₂/SiO₂ using a fluidized bed reactor. In the non-catalytic gasification, the product distribution was not influenced by the presence of H₂S. Steam reforming Ni catalyst was effective for the tar removal without H₂S addition, however, the addition of H₂S deactivated drastically. In contrast, Rh/CeO₂/SiO₂ exhibited higher and more stable activity than the Ni catalyst even under the presence of high concentration of H₂S (280 ppm). On the Ni catalyst, the adsorption of sulfur was observed by XPS and Ni species was oxidized during the partial oxidation of tar. In the case of Rh/CeO₂/SiO₂, the adsorption of sulfur was below the detection limit of XPS. This can be related to the self-cleaning of catalyst surface during the circulation in the fluidized bed reactor for the partial oxidation of tar derived from cedar pyrolysis.     

Effects of tar model compounds on commercial water gas shift catalysts

One attractive application of the catalytic water gas shift (WGS) reaction is the production of a syn-gas with high hydrogen concentration from gasification of solid combustibles. The catalyst's behavior can be affected by the hydrocarbons with high molecular weight (tar) still present in the gas after its purification. In this work the effect of some tar model compounds on two typical commercial WGS catalysts were investigated. A low temperature catalyst composed of Cu/Zn/Al and a high temperature catalyst based mainly on Fe and Cr were tested. N-hexadecane, fluorene, phenol, and octanol were used as tar model compounds. Besides these compounds, the effect of biodiesel was also investigated. In all cases a concentration of 0.5 g/Nm³ was used. Generally it was observed that a low concentration is often sufficient to produce a rapid deactivation. Catalysts were characterized by means of BET and XRD.     

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.     

Hydrogen generation in a downdraft moving bed gasifier coupled to a molten carbonate fuel cell

This paper describes the steady-state simulation of a moving bed downdraft gasifier which allows the conversion of agricultural biomass into a hydrogen-rich gas mixture so that it has an adequate composition for being used as a feedstock in a molten carbonate fuel cell (MCFC). In order to emphasize the applicability of the results, fuel specifications for a 250 kW MCFC (HM-300, MTU, Friedrichshafen, Germany) was used as a reference. The final design makes possible to produce 350 Nm³/h of a biogas in a vessel of 0.8 m diameter × 2.5 m height capable of treating 50 kg/h of dry biomass using 45 Nm³/h of air at 800 K and 1 bar.     

Bench-scale production of liquid fuel from woody biomass via gasification

The bench-scale production of hydrocarbon liquid fuel was achieved from woody biomass via gasification. The daily production capacity of the biomass-to-liquid (BTL) plant used in this study was 7.8 L of hydrocarbon liquid from 48 kg of woody biomass (on a dry basis), corresponding to 0.05 barrels. The BTL process involved the following steps: oxygen-enriched air gasification of the woody biomass, wet and dry gas cleaning, gas compression, carbon dioxide removal, and the Fischer-Tropsch (FT) synthesis reaction. In the gasification step, oxygen-enriched air gasification was carried out using a downdraft fixed-bed gasifier. The content of oxygen, which acts as the gasifying agent, was increased from 21.0 to 56.7 vol%; maximum values of the conversion to gas on a carbon basis and cold gas efficiency-approximately 96 C-mol% and 87.8%, respectively-were obtained at an oxygen content of around 30 vol%. With the increased oxygen content, the concentrations of CO, H₂, and CO₂ increased from 22.8 to 36.5 vol%, from 16.8 to 28.1 vol%, and from 9.8 to 14.8 vol%, respectively, while that of N₂ decreased from 48.8 to 16.0 vol%. The feed gas for the FT synthesis reaction was obtained by passing the product gas from the gasification step through a scrubber, carbon dioxide removal tower, and desulfurization tower; its composition was 30.8 vol% CO, 25.2 vol% H₂, 0.9 vol% CO₂, 2.5 vol% CH₄, 40.6 vol% N₂, < 5 ppb H₂S, and < 5 ppb COS. The hydrocarbon fuel was synthesized in a slurry bed reactor using hexadecane as the solvent and a Co/SiO₂ catalyst. For hydrocarbons with carbon chain lengths of more than 5 carbon atoms (collectively referred to as C₅₊) in the liquid fuel, a selectivity of 87.5% was obtained along with a chain growth probability of 0.84 under the following conditions: 4 MPa, 280 to 340 °C, and a ratio of catalyst weight to feed gas rate (W/F) of 9.3 g·h/mol.     

Experimental and kinetic study of the NO-reduction by tar formed from biomass gasification, using benzene as a tar model component

The present work studies the combustion of biomass syngas to characterize the NO-reduction by tar, benzene being selected as the representative model tar component. Experiments were carried out in a tubular flow reactor at atmospheric pressure and at different operating conditions i.e. an equivalence ratio of 0.5 to 2.5, temperatures between 1173 K and 1673 K and a reaction residence time of 50 to 100 ms. Kinetic parameters were determined from the experimental results. A simplified scheme of NO-reduction by benzene was presented and the effects of operating variables were concluded. The NO conversion is favored by an oxygen-rich condition, and the reduction efficiency falls with the rise of equivalence ratio, especially in the range of 0.5-1.0. Although high temperature enhances the reduction reactions, soot formation at high temperatures (1573 K, 1673 K) will seriously hinder the reduction of NO, which should be prevented. The ideal temperature is about 1473 K. 50 ms is found to be an insufficient residence time for the reduction. An increased contact time is of higher benefit at 1673 K where the heterogeneous reactions between NO and graphitized heavy hydrocarbons have a lower reaction rate. High pre-exponential factors and low activation energies are achieved under oxygen-rich conditions.     

Integrated high temperature gas cleaning: Tar removal in biomass gasification with a catalytic filter

A nickel-based catalytic filter material for the use in integrated high temperature removal of tars and particles from biomass gasification gas was tested in a broad range of parameters allowing the identification of the operational region of such a filter. Small-scale porous alumina filter discs, loaded with approximately 2.5 wt% Al₂O₃, 1.0 wt% Ni and 0.5 wt% MgO were tested with a particle free synthetic gasification gas with 50 vol% N₂, 12 vol% CO, 10 vol% H₂, 11 vol% CO₂, 12 vol% H₂O, 5 vol% CH₄ and 0–200 ppm H₂S, and the selected model tar compounds: naphthalene and benzene. At a typical face velocity of 2.5 cm/s, in the presence of H₂S and at 900 °C, the conversion of naphthalene is almost complete and a 1000-fold reduction in tar content is obtained. Technically, it would be better to run the filter close to the exit temperature of the gasifier around 800–850 °C. At 850 °C, conversions of 99.0% could be achieved in typical conditions, but as expected, only 77% reduction in tars was achieved at 800 °C.

Conversion data can be reasonably well described with first order kinetics and a dominant adsorption inhibition of the Ni sites by H₂S. The apparent activation energies obtained are similar to those reported by other investigators: 177 kJ/mol for benzene and 92 kJ/mol for naphthalene. The estimated heat of adsorption of H₂S is 71 kJ/mol in the benzene experiments and 182 kJ/mol in the naphthalene experiments, which points at very strong adsorption of H₂S. Good operation of the present material can hence only be guaranteed at temperatures above 830 °C mainly due to the strong deactivation by H₂S at lower temperatures.     

Conversion of Biomass Based Slurry in an Entrained Flow Gasifier

A two‐step process, BIOLIQ, with pyrolysis and subsequent entrained flow gasification has been developed at the Forschungszentrum Karlsruhe to produce synfuel from biomass. Experiments in a 60 kW pilot‐scale atmospheric entrained flow gasifier allow quantitative evaluation of the combustion behavior of biomass‐based slurry, leading to a better understanding of the gasification process.     

Catalytic reforming of tar during gasification. Part II. Char as a catalyst or as a catalyst support for tar reforming

Char, char-supported catalysts and ilmenite were investigated for the steam reforming of biomass tar derived from the pyrolysis of mallee wood in situ. Special attention was given to the reforming of aromatic ring systems in tar. The results indicated that the char-supported iron/nickel catalysts exhibited much higher activity for the reforming of tar than the char itself. Ilmenite and the char-supported iron catalyst contained similar active phase but showed different tar reforming activities. Kinetic compensation effects demonstrated that the reaction pathways on the char-supported catalysts were similar but were different from those on ilmenite. The proprieties of support could play important roles for the activities of the catalysts and the reaction pathways on the catalysts. Char would not only disperse the catalysts but also interact with the catalysts to enhance their activity for the steam reforming of tar.     

Sulphur poisoning of nickel-based hot gas cleaning catalysts in synthetic gasification gas: I. Effect of different process parameters

The effect of different process parameters on sulphur poisoning of nickel catalysts in tar (toluene), ammonia and methane decomposition was studied. Tests were carried out in a fixed-bed tube reactor at 800–1000°C at 5 and under 20 bar total pressure using a synthetic gasification gas mixture. In the same conditions, sulphur affected less the toluene and methane decomposing activity than the ammonia decomposing activity. Ammonia conversion was affected by the catalyst type but not by the nickel content of catalyst. When temperature was increased the effect of sulphur poisoning was decreased. At 20 bar pressure the poisoning effect of sulphur was stronger than at 5 bar pressure. To prevent sulphur poisoning of nickel catalysts in the tar and ammonia decomposition process at high pressure (20–30 bar), the catalyst process should operate at > 900°C. In addition, by decreasing the space velocity of the process the sulphur poisoning effect could be compensated in the test conditions.     

Sulphur poisoning of nickel-based hot gas cleaning catalysts in synthetic gasification gas II. Chemisorption of hydrogen sulphide

The effect of different components of gasification gas on sulphur poisoning of nickel catalysts were studied. In addition, the sulphur distribution and content of nickel catalyst beds were analysed to account the poisoning effect of sulphur on the activity of catalysts to decompose tar, ammonia and methane. The desorption behaviour of chemisorbed sulphur from the bed materials was monitored by temperature programmed hydrogenation (TPH). It was established that bulk nickel sulphide was active in decomposing ammonia in high-temperature gasification gas-cleaning conditions. The decomposing activity of methane was not affected by bulk nickel sulphide formation, but that of toluene was decreased. The activity of the catalyst regained rapidly when H₂S was removed from the gas. However, the conversion of ammonia was not regained at as high a level as before sulphur addition, most probably due to irreversible sulphur adsorption on the catalyst. The temperature increase could also be used to regenerate the catalyst performance especially in respect to methane and toluene. Sulphur adsorbed on nickel catalysts in different chemical states depends on the process conditions applied. At >900°C the sulphur adsorbed on the catalyst formed an irreversible monolayer on the catalyst surfaces, while at <900°C the adsorbed sulphur, probably composed of polysulphides (multilayer sulphur), was desorbed from the catalyst in sulphur-free hydrogen containing atmosphere. However, a monolayer of sulphur still remained on the catalyst after desorption. The enhanced effect of high total pressure on sulphur-poisoning of nickel catalysts could be accounted for the increased amount of sulphur, probably as a mode of polysulphides, adsorbed on the catalyst.     

Experimental and numerical investigation of tar destruction under partial oxidation environment

Tar in biomass product gas is a major problem because it reduces the reliability of the equipment and enhances pollutant emission. Partial oxidation is effective for reducing tar inside gasifiers. In order to predict tar reduction with partial oxidation technology, knowledge of the fate of tar during partial oxidation process is paramount.A continuous reactor was developed for tar destruction experiment under partial oxidation environment. Tar components and non-condensable gasses were measured and analyzed. Results show that the defined “primary tar” contents share about 60% of the total tar amounts. Phenolics prevail under initial reaction, but it is easy to form PAHs (polycyclic aromatic hydrocarbons) by polymerization reactions under certain ER (actual mass flow rate of oxygen/oxygen required for complete oxidation of biomass feed stock). This process results in an increase of tertiary tar. Hydrogen's evolution curve shows a steep rise with ER, which could be an indicator for the crack of secondary tar. A model was developed for describing partial oxidation of tar. Phenol, toluene, benzene and naphthalene were chosen as model compounds. Fluid flow, chemical mechanism and heat transfer are considered in the model. The calculated total tar amounts are in qualitative agreement with experimental results.     

Experimental measurement of gas concentration distribution in an impinging entrained-flow gasifier

On a laboratory-scale testing platform of impinging entrained-flow gasifier with two opposed burners, the detailed measurements of gas concentration distribution have been performed for carbonaceous compound (diesel oil) at atmospheric pressure. Under the condition of 1.48–2.36 O/C ratios (kg/kg), radial gas samples are collected at three axial positions and the syngas exit position with stainless steel water-cooled probes, the concentration distribution of the major gases (H₂, CO, CO₂, CH₄ and O₂) under stable operating state was determined with a mass spectrometry. These data are used to clarify mixing and reaction characteristics within the reactor, to give insight into the combustion process and provide a database for evaluating predictive mathematical models.