Electrochemical behaviour of propane-fed solid oxide fuel cells based on low Ni content anode catalysts

Two different low Ni content (10 wt.%) anode catalysts were investigated for intermediate temperature (800 °C) operation in solid oxide fuel cells fed with dry propane. Both catalysts were prepared by the impregnation of a Ni-precursor on different oxide supports, i.e. gadolinia doped ceria (CGO) and La_0.6Sr_0.4Fe_0.8Co_0.2O₃ perovskite, and thermal treated at 1100 °C for 2 h. The Ni-modified perovskite catalyst was mixed with a CGO powder and deposited on a CGO electrolyte to form a composite catalytic layer with a proper triple-phase boundary. Anode reduction was carried out in-situ in H₂ at 800 °C for 2 h during cell conditioning. Electrochemical performance was recorded at different times during 100 h operation in dry propane. The Ni-modified perovskite showed significantly better performance than the Ni/CGO anode. A power density of about 300 mW cm⁻² was obtained for the electrolyte supported SOFC in dry propane at 800 °C. Structural investigation of the composite anode layer after SOFC operation indicated a modification of the perovskite structure and the occurrence of a La₂NiO₄ phase. The occurrence of metallic Ni in the Ni/CGO system caused catalyst deactivation due to the formation of carbon deposits.     

Precious metal catalysts in the clean-up of biomass gasification gas Part 1: Monometallic catalysts and their impact on gasification gas composition

The performance of Rh, Ru, Pt, and Pd on modified commercial zirconia support (m-ZrO₂) was compared to a benchmark Ni/m-ZrO₂ catalyst in the presence of H₂S in the clean-up of gasification gas from tar, methane, and ammonia. The aim was to produce ultra clean gas applicable for liquid biofuel production. In general, the activity towards the decomposition decreased in the order of aromatic hydrocarbons, ethylene > methane > ammonia. Hydrocarbon decomposition on m-ZrO₂ supported Rh, Ni, and Ru catalysts mainly occurred at 800-900 °C through reforming and/or dealkylation reactions. Aromatic hydrocarbon decomposition reactions proceeded on Pt/m-ZrO₂ and Pd/m-ZrO₂ via oxidation reactions at temperatures of 600-800 °C, while at 900 °C, the reforming and/or dealkylation reactions were dominating also on Pt/m-ZrO₂ and Pd/m-ZrO₂ catalysts. During longer test runs of ten hours at 800 °C, the activity of the Rh/m-ZrO₂ catalyst declined in the presence of 100 ppm H₂S due to the sulfur poisoning effects, coke formation, and the particle size growth. Although the performance of Rh/m-ZrO₂ declined, it still remained better than Ni/m-ZrO₂ both towards naphthalene and total aromatic hydrocarbon, while only Ni/m-ZrO₂ and Ru/m-ZrO₂ decomposed ammonia in the presence of sulfur. Nevertheless, the most promising catalyst for clean gas production was Rh/m-ZrO₂.     

Precious metal catalysts in the clean-up of biomass gasification gas part 2: Performance and sulfur tolerance of rhodium based catalysts

Rh, Pt, and Pt-Rh catalysts on modified commercial zirconia support (m-ZrO₂) were screened for the clean-up of gasification gas from tar, methane, and ammonia both in the absence and presence of H₂S while varying the Rh metal content from 0.5 to 5 w-%. Our goal was to optimize the composition of the Rh/m-ZrO₂ catalyst in view of the production of ultra clean gas applicable for liquid biofuels synthesis. In the presence of 100 ppm sulfur, increasing Rh concentration from 0.5 to 5 w-% did not greatly improve the activity of the catalyst. The bimetallic Pt/Rh/m-ZrO₂ catalyst was also less active than the 0.5 w-% Rh/m-ZrO₂ catalyst. Furthermore, the Rh/m-ZrO₂ catalyst regained its performance at the set point of 800 °C when the sulfur feed was turned off even after exposures to 500-1000 ppm sulfur. Our data allow us to suggest that in the presence of sulfur, the active sites responsible for the reforming reactions are poisoned, but less impact occurs on sites responsible for oxidation reactions. Furthermore, the screening experiments allow to suggest that the Rh/m-ZrO₂ catalyst could be applicable to hot gas cleaning in the presence of sulfur (> 50 ppm) at above 800 °C using a moderate gas hourly space velocity of approximately 3400 1/h. Since biomass gasification gas generally contains sulfur, the 0.5 w-% Rh/m-ZrO₂ catalyst could be a promising option for gasification gas clean-up applications at temperatures above 800 °C where it reduces tar to very low levels.     

Coffee husks gasification using high temperature air/steam agent

Analyses made on the world's biomass energy potential show that biomass energy is the most abundant sustainable renewable energy. The available technical biomass energy potential surpasses the total world's consumption levels of petroleum oils, coal and natural gas. In order to achieve a sustainable harnessing of the biomass energy potential and to increase its contribution to the world's primary energy consumption, there is therefore a need to develop and sustain contemporary technologies that increase the biomass-to-energy conversion. One such technology is the high temperature air/steam gasification (HTAG) of biomass. In this paper we present findings of gasification experimental studies that were conducted using coffee husks under high temperature conditions. The experiments were performed using a batch facility, which was maintained at three different gasification temperatures of 900 °C, 800 °C, and 700 °C. The study findings exhibited the positive influence of high temperature on increasing the gasification process. Chars left while gasifying at 800 °C and 700 °C were respectively 1.5 and 2.4 times that for the case of 900 °C. Furthermore, increased gasification temperature led to a linear increment of CO concentration in the syngas for all gasification conditions. The effect was more pronounced for the generally poorly performing gasification conditions of N₂ and 2% oxygen concentration. When gasification temperature was increased from 700 °C to 900 °C the CO yield for the 2% O₂ concentration increased by 6 times and that of N₂ condition by 2.5 times. The respective increment for the 3% and 4% O₂ conditions were only twofold. This study estimated the kinetic parameters for the coffee husks thermal degradation that exhibited a reaction mechanism of zero order with apparent activation energy of 161 kJ/mol and frequency factor of 3.89 × 10⁴/min.     

Changes in char reactivity and structure during the gasification of a Victorian brown coal: Comparison between gasification in O2 and CO2

Char reactivity is an important factor influencing the efficiency of a gasification process. As a low-rank fuel, Victorian brown coal with high gasification reactivity is especially suitable for use with gasification-based technologies. In this study, a Victorian brown coal was gasified at 800 °C in a fluidised-bed/fixed-bed reactor. Two different gasifying agents were used, which were 4000 ppm O₂ balanced with argon and pure CO₂. The chars produced at different gasification conversion levels were further analysed with a thermogravimetric analyser (TGA) at 400 °C in air for their reactivities. The structural features of these chars were also characterised with FT-Raman/IR spectroscopy. The contents of alkali and alkaline earth metallic species in these chars were quantified. The reactivities of the chars prepared from the gasification in pure CO₂ at 800 °C were of a much higher magnitude than those obtained for the chars prepared from the gasification in 4000 ppm O₂ also at 800 °C. Even though both atmospheres (i.e. 4000 ppm O₂ and pure CO₂) are oxidising conditions, the results indicate that the reaction mechanisms for the gasification of brown coal char at 800 °C in these two gasifying atmospheres are different. FT-Raman/IR results showed that the char structure has been changed drastically during the gasification process.     

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.     

Behaviour of dolomite, olivine and alumina as primary catalysts in air-steam gasification of sewage sludge

Sewage sludge gasification assays were performed in an atmospheric fluidised bed reactor using air and air-steam mixtures as the gasifying agents. Dolomite, olivine and alumina are three well known tar removal catalysts used in biomass gasification processing. However, little information is available regarding their performance in sewage sludge gasification. The aim of the current study was to learn about the influence of these three catalysts in the product distribution and tar production during sewage sludge gasification. To this end, a set of assays was performed in which the temperature (750-850 °C), the in-bed catalyst content (0, 10 and 15 wt.%) and the steam-biomass ratio (SB) in the range of 0-1 were varied with a constant equivalence ratio (ER) of 0.3. The results were compared to the results from gasification without a catalyst. We show that dolomite has the highest activity in tar elimination, followed by alumina and olivine. In addition to improving tar removal, the presence of water vapour and the catalysts increased the content of H₂ in the gases by nearly 60%.     

Catalytic clean-up of gasification gas with precious metal catalysts - A novel catalytic reformer development

Several precious metal catalysts were prepared on modified zirconia and tested for the selective catalytic clean-up of the gasification gas. The activity of the precious metal catalysts were compared to that of the modified zirconia supported nickel catalyst and to the support. The activities of the catalysts were tested in a monolithic form in a quartz laboratory reactor at temperatures of 600-900 °C under atmospheric pressure using synthetic sulfur containing gas mixture. In addition, the stability of the Ni and Rh catalysts was examined by measuring the activities at 800 °C for 10 h using sulfur containing gas. The simulated gas contained CO, CO₂, CH₄, C₂H₄, H₂, N₂, H₂O, H₂S, NH₃ and a tar model compound, i.e. a mixture of naphthalene and toluene. The addition of metal on the support promoted the activity in tar model compound decomposition only at the temperature range of 850-900 °C. The order of activity was Rh ≈ Ni > Pd > Ir > Ru > Pt. Almost complete tar model compound conversion was achieved with Rh, as well as with Ni, at 900 °C. At lower temperatures, the support showed higher activity in tar model compound decomposition compared to the metal/support catalysts tested. Only Ni and Ru showed moderate activity in ammonia decomposition. In regard to sulfur tolerance at 800 °C, Rh was activated during the 10 h experiment while the activity of Ni decreased. The performance of both was restored after the overnight N₂ flush and the conversion of the tar model compound was higher for Rh (64%) than for Ni (46%).     

Pyrolysis-gasification of plastics, mixed plastics and real-world plastic waste with and without Ni-Mg-Al catalyst

Polypropylene, polystyrene, high density polyethylene and their mixtures and real-world plastic waste were investigated for the production of hydrogen in a two-stage pyrolysis-gasification reactor. The experiments were carried out at gasification temperatures of 800 or 850 °C with or without a Ni-Mg-Al catalyst. The influence of plastic type on the product distribution and hydrogen production in relation to process conditions were investigated. The reacted Ni-Mg-Al catalysts were analyzed by temperature-programmed oxidation and scanning electron microscopy. The results showed that lower gas yield (11.2 wt.% related to the mass of plastic) was obtained for the non-catalytic non-steam pyrolysis-gasification of polystyrene at the gasification temperature of 800 °C, compared with the polypropylene (59.6 wt.%) and high density polyethylene (53.5 wt.%) and waste plastic (45.5 wt.%). In addition, the largest oil product was observed for the non-catalytic pyrolysis-gasification of polystyrene. The presence of the Ni-Mg-Al catalyst greatly improved the steam pyrolysis-gasification of plastics for hydrogen production. The steam catalytic pyrolysis-gasification of polystyrene presented the lowest hydrogen production of 0.155 and 0.196 (g H₂/g polystyrene) at the gasification temperatures of 800 and 850 °C, respectively. More coke was deposited on the catalyst for the pyrolysis-gasification of polypropylene and waste plastic compared with steam catalytic pyrolysis-gasification of polystyrene and high density polyethylene. Filamentous carbons were observed for the used Ni-Mg-Al catalysts from the pyrolysis-gasification of polypropylene, high density polyethylene, waste plastic and mixed plastics. However, the formation of filamentous carbons on the coked catalyst from the pyrolysis-gasification of polystyrene was low.     

Air-steam gasification of sewage sludge in a bubbling bed reactor: Effect of alumina as a primary catalyst

Numerous references can be found in scientific literature regarding biomass gasification. However, there are few works related to sludge gasification. A study of sewage sludge gasification process in a bubbling fluidised bed gasifier on a laboratory scale is here reported. The aim was to find the optimum conditions for reducing the production of tars and gain more information on the influx of different operating variables in the products resulting from the gasification of this waste. The variables studied were the equivalence ratio (ER), the steam-biomass ratio (SB) and temperature. Specifically, the ER was varied from 0.2 to 0.4, the SB from 0 to 1 and the temperature from 750 °C (1023 K) to 850 °C (1123 K). Although it was observed that tar production could be considerably reduced (up to 72%) by optimising the gasification conditions, the effect of using alumina (aluminium oxide, of proven efficacy in destroying the tar produced in biomass gasification) as primary catalyst in air and air-steam mixture tests was also verified. The results show that by adding small quantities of alumina to the bed (10% by weight of fed sludge) considerable reductions in tar production can be obtained (up to 42%) improving, at the same time, the lower heating value (LHV) of the gas and carbon conversion.     

Experimental study on sawdust air gasification in an entrained-flow reactor

Experiments were performed in an entrained-flow reactor to better understand the processes involved in biomass air gasification. Effects of the reaction temperatures (700 °C, 800 °C, 900 °C and 1000 °C), residence time and the equivalence ratio in the range of 0.22-0.34 on the gasification process were investigated. The behavior of biomass gasification was discussed in terms of composition of produced gas. Four parameters, i.e. the low heating value, fuel gas production, carbon conversion and cold gas efficiency were used to evaluate the gasification. The results show that CO, CO₂ and H₂ are the main gasification products, while hydrocarbons (CH₄ and C₂H₄) are the minor ones. With the increase of the reaction temperature, the concentration of CO decreases, while the concentrations of CO₂ and H₂ increase. The concentrations of CH₄ and C₂H₄ reach their maximum value when the reaction temperature is 800 °C. The optimal reaction temperature is considered to be 800 °C and the optimal equivalence ratio is 0.28 in that the low heating value of the produced gas, carbon conversion and cold gas efficiency achieve their maximum values. The kinetic parameters of sawdust air gasification are calculated basing on the Arrhenius correlation.     

Investigation on the reactions influencing biomass air and air/steam gasification for hydrogen production

Hydrogen could be the energy carrier of the next world scene provided that its production, transportation and storage are solved. In this work the production of an hydrogen-rich gas by air/steam and air gasification of olive oil waste was investigated. The study was carried out in a laboratory reactor at atmospheric pressure over a temperature range of 700 ­ 900 °C using a steam/biomass ratio of 1.2 w/w. The influence of the catalysts ZnCl₂ and dolomite was also studied at 800 and 900 °C. The solid, energy and carbon yield (%), gas molar composition and high heating value of the gas (kJ NL^− 1), were determined for all cases and the differences between the gasification process with and without steam were established. Also, this work studies the different equilibria taking place, their predominance in each process and how the variables considered affect the final gas hydrogen concentration. The results obtained suggest that the operating conditions were optimized at 900 °C in steam gasification (a hydrogen molar fraction of 0.70 was obtained at a residence time of 7 min). The use of both catalysts resulted positive at 800 °C, especially in the case of ZnCl₂ (attaining a H₂ molar fraction of 0.69 at a residence time of 5 min).     

Pressurized gasification of woody biomass—Variation of parameter

Pressurized gas produced from biomass is a renewable resource that is attracting a great deal of attention due to its wide range of industrial applications, such as the production of hydrogen, chemicals or high grade fuels. Therefore, the Vienna University of Technology in cooperation with BioEnergy 2020+ is operating a bubbling pressurized gasification plant. The pressurized research unit (PRU) is able to perform the gasification of wood chips, wood pellets, coal and other solid fuels with gasification agents air, steam, oxygen or carbon dioxide. This paper gives the results of parameter variation at this plant with regard to the producer gas composition. The feedstock was wood pellets and as bed material olivine was used with an average particle size of 0.5 mm. The parameters varied were temperature (720-900 °C), pressure (1-5 bar), air ratio (0.2-0.4), gasification agent (air, steam, oxygen), biomass feed input (4.5-8 kg/h) and the fluidization conditions of the reactor fluidized bed (fluidization number (3-7)).     

The impact of carbon formation on Ni-YSZ anodes from biomass gasification model tars operating in dry conditions

The combination of solid oxide fuel cells (SOFCs) and biomass gasification has the potential to become an attractive technology for the production of clean and renewable energy. However the impact of tars, formed during biomass gasification, on the performance and durability of SOFC anodes has not been well established experimentally. This paper reports on an experimental study of the effects of carbon formation on the anodes of SOFC button cells from synthetic model tars arising from the gasification of biomass material. Furthermore the paper evaluates appropriate model tars to study the effects of typical biomass gasification tars on SOFC operation. The anode material used in this work was a 60:40 wt.% NiO/YSZ cermet, which was tested in a 15% H₂ gas mixture containing a concentration of 15 g/Nm³ of different biomass gasification model tars. Model tars included benzene and toluene representing the simplest and most predominant of biomass gasification tars, and a tar mix consisting of higher molecular weight tars such as naphthalene, pyrene, and phenol. It was found that carbon formation in dry conditions significantly damaged the anode of the fuel cell resulting in decreased cell performance and excessive anode polarization resistances. The higher reactivity of benzene compared to other model tars led to higher levels of carbon formation on reduced Ni-O catalysts. Different types of carbon were formed depending on the operating temperature of the SOFC.     

Catalytic test of supported Ni catalysts with core/shell structure for dry reforming of methane

Supported nickel catalysts with core/shell structures of Ni/Al₂O₃ and Ni/MgO-Al₂O₃ were synthesized under multi-bubble sonoluminescence (MBSL) conditions and tested for dry reforming of methane (DRM) to produce hydrogen and carbon monoxide. A supported Ni catalyst made of 10% Ni loading on Al₂O₃ and MgO-Al₂O₃, which performed best in the steam reforming of methane (97% methane conversion at 750 °C) and in the partial oxidation of methane (96% methane conversion at 800 °C), showed also good performance in DRM and excellent thermal stability for the first 150 h. The supported Ni catalysts Ni/Al₂O₃ and Ni/MgO-Al₂O₃ yielded methane conversions of 92% and 92.5%, respectively and CO₂ conversions of 95.0% and 91.8%, respectively, at a reaction temperature of 800 °C with a molar ratio of CH₄/CO₂ = 1. Those were near thermodynamic equilibrium values.     

The performances of higher alcohol synthesis over nickel modified K2CO3/MoS2 catalyst

Ni modified K₂CO₃/MoS₂ catalyst was prepared and the performance of higher alcohol synthesis catalyst was investigated under the conditions: T = 280–340 °C, H₂/CO (molar radio) = 2.0, GHSV = 3000 h^− 1, and P = 10.0 MPa. Compared with conventional K₂CO₃/MoS₂ catalyst, Ni/K₂CO₃/MoS₂ catalyst showed higher activity and higher selectivity to C₂⁺OH. The optimum temperature range was 320–340 °C and the maximum space-time yield (STY) of alcohol 0.30 g/ml h was obtained at 320 °C. The selectivity to hydrocarbons over Ni/K₂CO₃/MoS₂ was higher, however, it was close to that of K₂CO₃/MoS₂ catalyst as the temperature increased. The results indicated that nickel was an efficient promoter to improve the activity and selectivity of K₂CO₃/MoS₂ catalyst.     

Carbon infiltration of carbon-fiber preforms by catalytic CVI

Experimental studies were conducted to assess catalytic chemical vapor infiltration processing for preparing carbon/carbon composites as a potential improvement to conventional one. The catalyst was introduced into the carbon fiber preforms by wet impregnation. Using C₃H₆/Ar/H₂ as the original gas, catalytic carbon was formed at 500-1000 °C for 1-3 h. It was found that carbon filaments were formed as the preparing temperatures were 500-700 °C, and carbon particles could be obtained at 800-1000 °C. The increasing rate of density was up to 0.916 g/ml/h when the sample was formed at 600 °C for 1 h with the catalytic of 0.7 wt.% Ni, and the carbon yield arrived to 90 wt.% . According to the micrographs of catalytic carbon, the forming mechanism of carbon filaments agreed with that of carbon filaments due to a metal catalyst. The weighted average interlayer spacing of C/C composites with catalytic carbon decreased to 0.341.     

Novel carbon-supported Fe-N electrocatalysts synthesized through heat treatment of iron tripyridyl triazine complexes for the PEM fuel cell oxygen reduction reaction

2,4,6-Tris(2-pyridyl)-1,3,5-triazine (TPTZ) was used as a ligand to prepare iron-TPTZ (Fe-TPTZ) complexes for the development of a new oxygen reduction reaction (ORR) catalyst. The prepared Fe-TPTZ complexes were then heat-treated at temperatures ranging from 400 °C to 1100 °C to obtain carbon-supported Fe-N catalysts (Fe-N/C). These catalysts were characterized in terms of catalyst composition, structure, and morphology by several instrumental methods such as energy dispersive X-ray, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. With respect to the ORR activity, the Fe-N/C catalysts were also evaluated by cyclic voltammetry, as well as rotating disk and ring-disk electrodes. The results showed that among the heat-treated catalysts, that obtained at a heat-treatment temperature of 800 °C is the most active ORR catalyst. The overall electron transfer number for the catalyzed ORR was determined to be between 3.5 and 3.8, with 10-30% H₂O₂ production. The ORR catalytic activity of this catalyst was also tested in a hydrogen-air proton exchange membrane (PEM) fuel cell. At a cell voltage of 0.30 V, this fuel cell can give a current density of 0.23 A cm⁻² with a maximum MEA power density of 0.070 W cm⁻² indicating that this catalyst has potential to be used as a non-noble catalyst in PEM fuel cells.     

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.     

Hydrogen production via catalytic steam reforming of fast pyrolysis bio-oil in a two-stage fixed bed reactor system

Hydrogen production was prepared via catalytic steam reforming of fast pyrolysis bio-oil in a two-stage fixed bed reactor system. Low-cost catalyst dolomite was chosen for the primary steam reforming of bio-oil in consideration of the unavoidable deactivation caused by direct contact of metal catalyst and bio-oil itself. Nickel-based catalyst Ni/MgO was used in the second stage to increase the purity and the yield of desirable gas product further. Influential parameters such as temperature, steam to carbon ratio (S/C, S/CH₄), and material space velocity (W_BHSV, GHSV) both for the first and the second reaction stages on gas product yield, carbon selectivity of gas product, CH₄ conversion as well as purity of desirable gas product were investigated. High temperature (> 850 °C) and high S/C (> 12) are necessary for efficient conversion of bio-oil to desirable gas product in the first steam reforming stage. Low W_BHSV favors the increase of any gas product yield at any selected temperature and the overall conversion of bio-oil to gas product increases accordingly. Nickel-based catalyst Ni/MgO is effective in purification stage and 100% conversion of CH₄ can be obtained under the conditions of S/CH₄ no less than 2 and temperature no less than 800 °C. Low GHSV favors the CH₄ conversion and the maximum CH₄ conversion 100%, desirable gas product purity 100%, and potential hydrogen yield 81.1% can be obtained at 800 °C provided that GHSV is no more than 3600 h^− 1. Carbon deposition behaviors in one-stage reactor prove that the steam reforming of crude bio-oil in a two-stage fixed bed reaction system is necessary and significant.