Recent progress in Japan on hot gas cleanup of hydrogen chloride, hydrogen sulfide and ammonia in coal-derived fuel gas

The present review paper highlights on the recent progress in Japan on the hot gas cleanup of HCl, H₂S and NH₃ in raw fuel gas for coal-based, combined cycle power generation technologies. It has been shown that NaAlO₂, prepared by mixing Na₂CO₃ solution with Al₂O₃ sol, can reduce HCl in an air-blown gasification gas from the initial 200 ppm to < 1 ppm at 400 °C, and it is tolerable for 200 ppm H₂S. With regard to the removal of H₂S, studies on the stability and durability of ZnFe₂O₄ sorbent in a simulated fuel gas have indicated the presence of an optimal operation temperature from the viewpoint of the suppression of both vaporization of metallic Zn and carbon formation from CO. High-performance TiO₂-supported ZnFe₂O₄, which can decrease 1000 ppm H₂S to < 1 ppm at 450 °C and 1 MPa, has been developed by the homogeneous precipitation method using a mixture of SiO₂ sol and an aqueous solution of Zn and Fe nitrates, followed by mixing with TiO₂. Although this sorbent is regenerable and durable, the sorption ability should be improved in a syngas-rich fuel gas from an O₂-blown gasifier. A novel method to prepare carbon-supported ZnFe₂O₄ and CaFe₂O₄ by impregnating the corresponding nitrate solution with brown coal has been proposed, and the large desulfurization capacity of almost 100% has been achieved in the removal of 4000 ppm H₂S around 450 °C. The present authors have demonstrated that an Australian limonite rich in α-FeOOH is practically feasible as the catalyst material for the decomposition of 2000 ppm NH₃ in a syngas-rich gas of 25 vol.% H₂/50 vol.% CO at 750 °C, because small amounts of H₂O and CO₂ added to the gas can work efficiently for inhibiting carbon deposition from the CO.     

Sulfur transfers from pyrolysis and gasification of direct liquefaction residue of Shenhua coal

The sulfur transformation during pyrolysis and gasification of Shenhua direct liquefaction residue was studied and the release of H₂S and COS during the process was examined. For comparison, the sulfur transfer of Shenhua coal during pyrolysis and that of pyrolyzed char during gasification were also studied. The residue was pyrolyzed at 10 °C /min to 950 °C. During pyrolysis about 33.6% of sulfur was removed from the residue, among which 32.1% was formed H₂S in gas and 1.5% was transferred into tar, 66.4% of the sulfur was remained in residue char. Compared with coal, the residue has generated more H₂S due to presence of Fe_1−xS which was enriched in residue during liquefaction process. There is a few COS produced at 400-500 °C during pyrolysis of coal, but it was not detected form pyrolysis of the residue. During CO₂ gasification, compared with pyrolysis and steam gasification, there are more COS and less H₂S formation, because CO could react with sulfide to form COS. During steam gasification only H₂S was produced and no COS detected, because H₂ has stronger reducibility to form H₂S than CO. After steam gasification no sulfur was detected in the gasification residue. The XRD patterns show after steam gasification, only Fe₃O₄ is remained in the gasification residue. This indicates that the catalyst added during the liquefaction of coal completely reacted with steam, resulting in the formation of H₂ and Fe₃O₄.     

NH3 and HCN formation during the gasification of three rank-ordered coals in steam and oxygen

A Victorian brown coal (68.5% C), a Chinese high-volatile Shenmu bituminous coal (82.3% C) and a Chinese low-volatile Dongshan bituminous coal (90% C) were gasified in a fluidised-bed/fixed-bed reactor at 800 °C in atmospheres containing 15% H₂O, 2000 ppm O₂ or 15% H₂O + 2000 ppm O₂. While the gasification of these coals in 2000 ppm O₂ converted less than 27% of coal-N into NH₃, the introduction of steam played a vital role in converting a large proportion of coal-N into NH₃ by providing H on char surface. The importance of the roles of steam in the formation of NH₃ in atmospheres containing 15% H₂O + 2000 ppm O₂ decreased with increasing coal rank. This is largely due to the slow gasification of high-rank coal chars, resulting in low availability of H on char surface. The gasification of chars from the high-rank coal appears to produce higher yields of HCN than that of lower rank coals, probably as a result of the decomposition of partially hydrogenated/broken/activated char-N structures during gasification at high temperature. The alkali and alkaline earth metallic species in brown coal tend to favour the release of coal-N as tar-N but have limited effects on char-N conversion during gasification.     

The effect of water on the activation and the CO2 capture capacities of alkali metal-based sorbents

Alkali metal-based sorbents were prepared by the impregnation either of potassium carbonate (K₂CO₃) or of sodium carbonate (Na₂CO₃) on the supports (activated carbon (AC) and Al₂O₃). The CO₂ absorption and regeneration properties were measured in a fixed bed reactor at the low temperature conditions (CO₂ absorption at 60 ‡C and regeneration at 150 °C). The potassium carbonate which was supported on the activated carbon (K₂CO₃/AC) was clarified as a leading sorbent, of which the total CO₂ capture capacity was higher than those of other sorbents. This sorbent was completely regenerated and transformed to its original phase by heating the used sorbent. The activation process before CO₂ absorption needed moisture nitrogen containing 1.3–52 vol% H₂O for 2 hours either at 60 ‡C or at 90 °C. The activation process played an important role in CO₂ absorption, in order to form new active species defined as K₂CO₃· 1.5 H₂O, by X-ray diffraction. It was suggested that the new active species (K₂CO₃·1.5H₂O) could be formed by drying the K₄H₂(CO₃)3·1.5H₂O phase formed after pre-treatment with excess water.     

Nano-sized carbon hollow spheres for abatement of ethylene

In this paper, the ethylene adsorption capacities of the nano-sized carbon hollow spheres (CNB) and active carbon (AC), the Pd (PdCl₂) impregnated CNB or AC (Pd/CNB, Pd/AC) and heat treatment under various conditions, were studied at different ethylene concentrations from 64 to 1060 ppm. The results indicated that AC had a good ethylene adsorption capacity at high ethylene concentration. Pd impregnation decreased the ethylene adsorption capacity of AC. Heat treatment and H₂ activation could increase the ethylene adsorption capacity, but also lowered than AC itself. CNB had lower ethylene adsorption capacity than AC, but heat treatment and H₂ activation could increase its ethylene adsorption capacity markedly. With activating condition from heat treatment in N₂ at 300 °C to activation in H₂/N₂ at 100 °C, to activation in H₂ at 200 °C, and to activation in H₂ at 300 °C, the ethylene adsorption capacity of Pd/CNB was increased regularly. At low ethylene concentration, viz., 64 ppm, the ethylene adsorption quantities (q _a) by Pd/CNB activated in H₂ at 200 or 300 °C were higher than any other adsorbents. So, activated in H₂ atmosphere at higher than 100 °C, Pd/CNB is particularly advantaged for adsorbing low concentration of ethylene. Amongst all the adsorbents used, Pd/CNB activated in H₂ atmosphere at 300 °C for 2 h has the highest ethylene adsorption capacity at lower concentration than 125 ppm. In addition, all the CNB, Pd/CNB, AC, and Pd/AC samples can be easily regenerated in airflow for more than 3 h.     

Microwave absorption properties of Ni0.6Zn0.4Fe2O4 composites with nonmagnetic nanoferrite percentages

Microwave absorption materials need to be thin and lightweight and possess strong wave absorption ability and a wide absorption frequency band. To satisfy these conditions, we changed the microstructure of the composite by mixing ferrite material with different particle sizes. Specifically, we mixed nanosized nonmagnetic ZnFe₂O₄ powder into Ni_0.6Zn_0.4Fe₂O₄ powder, investigated the microwave absorption properties depending on the packing fraction. The crystal structure of the synthesized ferrite powders was analyzed through XRD, and the particle size was analyzed using a PSA and SEM. The density of the powders, which is required to measure the packing fraction, was determined via the gas disposition method, and the magnetic properties of the composites were analyzed using a VSM. The reflection loss represents the electromagnetic wave absorption characteristics, and it was calculated by substituting the measured permittivity and permeability values, into the equation based on the transmission line theory. The Ni_0.6Zn_0.4Fe₂O₄/ZnFe₂O₄ composite showed 99.9% absorption with a high packing fraction, and the absorption peak shifted to high frequencies. These characteristics suggest that the absorption ability and frequency range of the electromagnetic-wave-shielding composite can be easily controlled. Because of the high-absorption characteristic, absorption frequency control, and cost effectiveness, this composite can be applied to products such as thin electromagnetic-wave-shielding sheets.     

Atomic hydrogenation-induced paramagnetic-ferromagnetic transition in zinc ferrite

A paramagnetic-ferromagnetic transition was observed in normal spinel zinc ferrite (ZnFe₂O₄) during atomic hydrogenation at room temperature. Magnetic measurements showed enhanced ferromagnetic property with increasing hydrogenation time. The hydrogenated ZnFe₂O₄ has normal spinel structure according to X-ray diffraction (XRD) and Raman analyses. Iron hydride was found from the XRD and X-ray absorption fine structure results. No A–B site ions exchange was observed in the x-ray absorption spectra while the atomic distances of Fe–O, Zn–O, Fe–Fe, Zn–Zn and Fe–Zn coordinations were reduced. A hybrid of Fe²⁺ and Fe³⁺ in hydrogenated ZnFe₂O₄ can be further revealed through deconvolution of x-ray absorption near edge structure. The paramagnetic-ferromagnetic transition and enhanced ferromagnetic property were mainly due to the formation of iron hydride and the B-site super-exchange interactions of Fe²⁺ and Fe³⁺.     

Preparation and electromagnetic properties of nanosized ZnFe2O4 with various shapes

In this paper, nanosized ZnFe₂O₄ with different morphologies were prepared by electrospinning method. The choice of initial parameters, such as PVP concentration, metal salt concentration, electrostatic voltage, calcination temperature and calcination rate, were investigated to prepare desired morphologies. The as-prepared samples exhibited various shapes of nano-particle, nano-rods, nano-beads and nano-fiber. The relationship between microstructure and electromagnetic properties was discussed in detail. It has been found that the saturation magnetization of ZnFe₂O₄ ferrite not changed significantly with the various morphologies and the values were nearly 13 emu/g. However, the coercivity was varied with the different morphologies, and the maximum value of 48.79 Oe was observed in the ZnFe₂O₄ nano-fiber. Moreover, the magnetic loss capacity of ZnFe₂O₄ was improved with the enhancement of the morphology anisotropy. The various shaped ZnFe₂O₄ can be promising lightweight microwave absorbers and it is significant to develop novel microwave absorption mechanism of ZnFe₂O₄ ferrite.     

Removal of sulfur at high temperatures using iron-based sorbents supported on fine coal ash

This paper deals with the simultaneous removal of H₂S and COS in the temperature range of 400-650 °C at 1 bar by using iron-based sorbents. The iron-based sorbents were prepared using iron oxide and cerium oxide with coal fine ash as the support. Simulated coal gas was used in the sulfidation experiments and 5% O₂ in N₂ gas was used for regeneration of sorbents. Both sulfidation and regeneration experiments have been carried out using a fixed-bed quartz reactor. The product gases were analyzed using a GC equipped with a TCD and a FPD. The results demonstrated that both H₂S and COS can be effectively reduced using the iron-based sorbents supported on fine coal ash. XRD analysis shows that Fe_1−xS phase has formed during sulfidation indicating a high sulfur capacity of the sorbent. The mechanism of the removal of COS simultaneously with H₂S is also discussed.     

Partial oxidation of methane and the effect of sulfur on catalytic activity and selectivity

Partial oxidation of methane into syngas was conducted over fresh and sulfided catalysts at a temperature range of 450–750 °C. The temperature dependence of conversion, H₂/CO ratio, and the CO₂ concentration were measured for both fresh and sulfided catalysts. Regardless of metal type, metal loading, support type, and the methods of preparation it appears that all the fresh catalysts were very active and conversions of higher than 70% with H₂/CO ratio of about 2 were observed at 750 °C. Pulse sulfidation appears to be reversible for some of the catalysts but not for all. Under pulse sulfidation conditions, the Rh(0.5%)/Al₂O₃ and NiMg₂O_x-1100 °C (solid solution) catalysts were fully regenerated after reduction with hydrogen. Rh catalyst showed the best overall activity, less carbon deposition, both fresh and when it was exposed to pulses of H₂S. Sulfidation under steady-state conditions, flowing H₂S/Ar mixture over the catalysts, significantly reduce catalyst activity. The catalysts were characterized before and after reaction with H₂S using temperature-programmed oxidation (TPO) and reduction (TPR), X-ray diffraction, and XPS.     

Studies on Fourier transform infrared spectroscopy,scanning electron microscope,and direct current conductivity of polyaniline doped zinc ferrite

In situ polymerization of aniline was carried out in the presence of zinc ferrite to synthesize polyaniline/ZnFe₂O₄ composites (PANI/ZnFe₂O₄) by chemical oxidation method. The composites have been synthesized with various compositions (10, 20, 30, 40, and 50 wt %) of zinc ferrite in PANI. From the Fourier transform infrared spectroscopy (FTIR) studies on polyaniline/ZnFe₂O₄ composites, the peak at 1140 cm⁻¹ is considered to be measure of the degree of electron delocalization. The surface morphology of these composites was studied with scanning electron micrograph (SEM). The dc conductivity has been studied in the temperature range from 40–160°C and supports the one‐dimensional variable range hopping (1DVRH) model proposed by Mott. The results obtained for these composites are of scientific and technological interest. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Iron(II) Sulfate(VI) from Titania Production as a Raw Material for Preparation of Hydrogen Sulfide Sorbents

A hybrid sorbent material for removal of hydrogen sulfide from air was developed. The material is based on activated carbon and iron compounds obtained from waste iron(II) sulfate(VI) heptahydrate. The iron salt is deposited on the carbonaceous support and subjected to oxidation (Fe²⁺ to Fe³⁺) using atmospheric oxygen under alkaline conditions. An effect of H₂O₂ addition to the process on the composition of the resultant material was also examined. X-ray diffraction (XRD) analyses confirmed easy conversion of waste FeSO₄·7H₂O to iron oxides Fe₃O₄ and FeOOH. The activated carbon supporting iron oxides revealed a higher efficiency in H₂S elimination from air compared to the commercial activated carbon, without any modification.     

Development of a pilot-scale acid gas removal system for coal syngas

The Korean pilot-scale gasification facility consists of a coal gasifier, hot gas filtering system, and acid gas removal (AGR) system. The syngas stream from the coal gasification at the rate of 100–120 Nm³/hr included pollutants such as fly ash, H₂S, COS, etc. The acid gas, such as H₂S and COS, is removed in the AGR system before generating electricity by gas engine and producing chemicals like Di-methyl Ether (DME) in the catalytic reactor. A hydrolysis system was installed to hydrolyze COS into H₂S. The designed operation temperature and pressure of the COS hydrolysis system are 150 °C and 8 kg/cm². After the hydrolysis system, COS was reduced below 1 ppm at the normal operating condition. The normal designed operation temperature and pressure of the AGR system are below 40 °C and 8 kg/cm². Fe-chelate was used as an absorbent. H₂S was removed below 0.5 ppm in the AGR system when the maximum concentration of H₂S was 900 ppm. A small scale COS adsorber was also installed and tested to remove COS below 0.5 ppm. COS was removed below 0.1 ppm after the COS adsorbents such as the activated carbon and ion exchange resin. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Removing H2S from Biogas Using Sorbents for Solid Oxide Fuel Cell Applications

Desulfurization of biogas is essential for its application in solid oxide fuel cells. The influence of CH₄, CO₂, H₂, and O₂ as well as the effect of moisture onto desulfurization performance of an activated carbon, an adsorbent based on a CuO‐MnO mixture, and a zeolite adsorbent were analyzed. The use of moisturized gas had no negative influence on the H₂S adsorption performance of activated carbon. The CuO‐MnO sorbent showed the best performance, but the presence of moisture had a negative influence. The performance of zeolite dropped for three gas mixtures, while for two other mixtures moisture had little to no influence on H₂S adsorption performance.     

活性炭纤维吸附稀溶液中SCN-的电化学再生

为了研究电化学再生活性炭纤维（ACF）的效果,以SCN^-为模型物,通过测量再生后活性炭纤维对SCN^-的吸附容量的大小,考察了时间、吸附质浓度、再生循环次数等再生过程中的影响因素。结果表明,适宜的再生条件为0.8 mA正极化2 h,0.5 mol·L^-1的硫酸溶液,能使再生后ACF的吸附容量提高为原始ACF的3倍。5次电化学再生循环后,ACF的吸附容量没有明显降低,再生后ACF纤维表面也没有明显损伤。     

One-step room-temperature solid-phase synthesis of ZnFe2O4 nanomaterials and its excellent gas-sensing property

ZnFe₂O₄ nanomaterials have been synthesized by simple one-step solid-phase chemical reaction between Zn(CH₃COO)₂·2H₂O, FeCl₃·9H₂O and NaOH within a very short time at room temperature. The solid-phase products were characterized by X-ray diffraction, energy-dispersive X-ray spectroscopy, thermogravimetic analysis, transmission electron microscopy and scanning electron microscopy. Results indicated that the particle size of product can be obviously let up and the agglomeration phenomenon can be improved by the surfactant. Moreover, the ZnFe₂O₄ nanomaterials were applied in gas sensor and exhibited much better sensing performance than bulk ZnFe₂O₄. The as-prepared ZnFe₂O₄ nanomaterials have high sensitivity, good selectivity and fast response/recovery characteristic for ethanol and hydrogen sulfide. The improved ZnFe₂O₄ nanomaterials have high response value of 21.5 and 14.8 for ethanol and hydrogen sulfide in the optimized operating temperature of 332 °C and 240 °C, respectively. The response and recovery time was found to be within 4 s and 14 s for ethanol, while 7 s and 25 s for hydrogen sulfide.     

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.     

Fuel processor integrated H2S catalytic partial oxidation technology for sulfur removal in fuel cell power plants

H₂S catalytic partial oxidation technology with an activated carbon catalyst was found to be a promising method for the removal of hydrogen sulfide from fuel cell hydrocarbon feedstocks. Three different fuel cell feedstocks were considered for analysis: sour natural gas, sour effluent from a liquid middle distillate fuel processor and a Texaco O₂-blown coal-derived synthesis gas. The H₂S catalytic partial oxidation reaction, its integratability into fuel cell power plants with different hydrocarbon feedstocks and its salient features are discussed. Experimental results indicate that H₂S concentration can be removed down to the part-per-million level in these plants. Additionally, a power law rate expression was developed and reaction kinetics compared to prior literature. The activation energy for this reaction was determined to be 34.4 kJ/g mol with the reaction being first order in H₂S and 0.3 order in O₂.     

Zinc ferrite based gas sensors: A review

Flammable, explosive and toxic gases, such as hydrogen, hydrogen sulfide and volatile organic compounds vapor, are major threats to the ecological environment safety and human health. Among the available technologies, gas sensing is a vital component, and has been widely studied in literature for early detection and warning. As a metal oxide semiconductor, zinc ferrite (ZnFe₂O₄) represents a kind of promising gas sensing material with a spinel structure, which also shows a fine gas sensing performance to reducing gases. Due to its great potentials and widespread applications, this article is intended to provide a review on the latest development in zinc ferrite based gas sensors. We first discuss the general gas sensing mechanism of ZnFe₂O₄ sensor. This is followed by a review of the recent progress about zinc ferrite based gas sensors from several aspects: different micro-morphology, element doping and heterostructure materials. In the end, we propose that combining ZnFe₂O₄ which provides unique microstructure (such as the multi-layer porous shells hollow structure), with the semiconductors such as graphene, which provide excellent physical properties. It is expected that the mentioned composites contribute to improving selectivity, long-term stability, and other sensing performance of sensors at room or low temperature.     

Modified bentonites as adsorbents of hydrogen sulfide gases

Carbonate-rich bentonite was modified by iron and copper chlorides in order to synthesize effective and cheap adsorbents for neutralization of H₂S in low-concentrated exhaust gases. Bentonite and modified bentonite were analysed using atomic absorption spectroscopy (AAS), X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and BET surface area analysis. In addition, bentonite and modified bentonite were tested as hydrogen sulfide adsorbents. Iron-containing material showed a significant improvement in the capacity for H₂S removal. The longest time of effective protective action (before H₂S appears on the outlet of the column) was obtained for the bentonite modified with copper hydroxide. The results indicated that on the surface of modified samples hydrogen sulfide reacts with metal hydroxide forming sulfides. Sulfided iron-containing sample could be regenerated by exposing it to the air.