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.     

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.     

Catalytic performance of supported Ni catalysts in partial oxidation and steam reforming of tar derived from the pyrolysis of wood biomass

Activity test of Ni/Al₂O₃, Ni/ZrO₂, Ni/TiO₂, Ni/CeO₂ and Ni/MgO catalysts in the partial oxidation (POT) and steam reforming of tar (SRT) derived from the pyrolysis of cedar wood was performed. In these activity tests, the order of the performance in both reactions was similar. Catalyst characterization was also carried out by means of H₂ adsorption, TPR and XRD. From the combination of catalyst characterization with the results of the activity tests, it is suggested that the conversion of tar in POT and SRT is mainly controlled by the number of surface Ni metal. In addition, Ni/CeO₂ showed smaller amount of coke than other catalysts in the POT and SRT. From the TGA profiles of active carbon mixed with catalysts, it is found that Ni/CeO₂ promoted the reaction of active carbon with O₂ and steam. The function of the fluidized bed reactor in the POT with respect to coke and tar amount was discussed.     

Performance of a catalytically activated ceramic hot gas filter for catalytic tar removal from biomass gasification gas

Silicon carbide-based filter elements were catalytically activated to provide filter elements for catalytic tar removal from biomass-derived syngas. The filter element support was coated with CeO₂, CaO–Al₂O₃ and MgO with a specific surface of 7.4, 15.9 and 21.9 m²/g synthesized by exo-templating with activated carbon. Doping of a MgO coated filter element with 60 wt% NiO has led to an increase of the specific surface from 0.15 to 0.21 m²/g, whereas in case of a MgO–Al₂O₃ coated filter element a decrease from 1.18 to 0.91 m²/g was found. An increase of the NiO loading from 6 to 60 wt% on a MgO coated filter element resulted in an increase of the naphthalene conversion from 91 to 100% at 800 °C and a face velocity of 2.5 cm/s at a naphthalene concentration of 5 g/Nm³ in model biomass gasification gas. In case of a MgO–Al₂O₃ coated filter element with 60 wt% NiO in addition to complete naphthalene conversion in the absence of H₂S, a higher conversion of 66% was found in the presence of 100 ppmv H₂S compared to 49% of the MgO–NiO coated filter element. After scaling up of the catalytic activation procedure to a 1520 mm long filter candle, which shows an acceptable differential pressure of 54.9 mbar, 58 and 97% naphthalene conversion was achieved in the presence and absence of H₂S, respectively. The calculated WHSV value of 209.6 Nm³ h⁻¹ kg⁻¹ indicates the technical feasibility of a further increase of the catalytic performance by an increase of the NiO loading.     

Development of Ni catalysts for tar removal by steam gasification of biomass

Catalytic performance of Ni/CeO₂/Al₂O₃ catalysts prepared by a co-impregnation and a sequential impregnation method in steam gasification of real biomass (cedar wood) was investigated. Especially, Ni/CeO₂/Al₂O₃ catalysts prepared by the co-impregnation method exhibited higher performance than Ni/Al₂O₃ and Ni/CeO₂/Al₂O₃ prepared by the sequential impregnation method, and the catalysts gave lower yields of coke and tar, and higher yields of gaseous products. The Ni/CeO₂/Al₂O₃ catalysts were characterized by thermogravimetric analysis, temperature-programmed reduction with H₂, transmission electron microscopy and extended X-ray absorption fine structure, and the results suggested that the interaction between Ni and CeO₂ became stronger by the co-impregnation method than that by sequential method. Judging from both results of catalytic performance and catalyst characterization, it is found that the intimate interaction between Ni and CeO₂ can play very important role on the steam gasification of biomass.     

Recent advances in catalysts for hot-gas removal of tar and NH3 from biomass gasification

Biomass gasification produces a low to medium-BTU product gas (or syngas) containing primarily CO₂, H₂, CO, CH₄ and (C₂ + C₃), as well as some contaminants such as tars, NH₃, H₂S and SO₂. In order to achieve better efficiencies of the syngas applications, these contaminants must be removed before the syngas is used for internal combustion, gas engines, and in particular for fuel cells and methanol synthesis. Compared with the wet scrubbing technology, hot-gas cleanup technology to remove tar, ammonia and other contaminants at the “hot” state is more advantageous with respect to energy efficiencies. This paper provides an overview on recent advances in catalysts for hot-gas removal of tar and ammonia from biomass gasification. The review focuses on the recent development and applications of dolomite catalysts, iron-based catalysts, nickel and other metal supported catalysts, and the novel carbon-supported catalysts for hot-gas tar removal and ammonia decomposition. The barriers in applications of hot-gas cleanup processes and catalysts for full-scale biomass gasification, and areas for future research, are also discussed.     

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.     

Hydrogen production by the partial oxidation and steam reforming of tar from hot coke oven gas

Hot coke oven gas (COG) with a temperature of about 1050 K was produced from a test unit for coke production, the capacity of which was 80 kg of coal. The COG was introduced into an experimental unit with a tar converter where oxygen and steam were injected. Over 98% of the total carbon in the hot COG was partially oxidized, reformed with steam and converted to hydrogen and CO. About 1 Nm³/h of hydrogen was continuously produced for 5 h in this experiment. The experimental results suggest that three to five times the amount of hydrogen and CO that were present in the original COG could be recovered by this technology, utilizing the heat of the hot COG for the reaction. The feasibility study showed that hydrogen can be produced by this technology at a lower cost and higher efficiency than by the separation of cold COG.     

Numerical analysis of flow field in the hot gas filter vessel during the pulse cleaning process

The flow field is simulated for a ceramic filter vessel containing three candle filters which are arranged in the form of an equilateral triangle. Grids generated by GAMBIT are adopted for the simulations. The Reynolds stress model provided by FLUENT code is applied to evaluate gas flow and temperature field in the filter vessel. The temperature profiles in the ceramic candle filter cavity during the pulse cleaning process are analyzed under different operating conditions and for different lengths of candle filter. The evolution of radial velocity in the porous wall of the filters being cleaned and the normal working filters as well as around the filters is discussed. Sharp temperature change takes place in the top of the candle filter which is subject to thermal stress. The phenomenon of temperature increase during the pulse cleaning process has been carefully observed and interpreted based on the effect of gas compression. The simulated results show qualitative agreement with the experimental field observations with the filter vessel.     

High-temperature removal of cadmium from a gasification flue gas using solid sorbents

In this work, the retention capacity of solid sorbents for cadmium species present in coal gasification flue gases at high temperature was investigated. The influence of HCl(g) on the gas atmosphere was also evaluated. The study was carried out in a laboratory scale reactor, using synthetic gas mixtures with the sorbent as fixed bed. The sorbents tested were kaolin, limestone, alumina and fly ashes. The results obtained were compared with data from the works of other authors, who used similar solid sorbents in typical coal combustion flue gases. Whereas in the combustion atmospheres described in the literature, kaolin, limestone and alumina showed high retention capacities for cadmium compounds (0.5-40 mg g⁻¹), in the coal gasification atmospheres studied in the present work, the amount of cadmium captured by these solid sorbents was negligible. Fly ashes were found to be the most efficient for retaining cadmium in gasification atmospheres, their maximum retention capacity in the conditions studied being approx 0.75 mg g⁻¹.     

Research progress of hot gas filtration,desulphurization and HCl removal in coal-derived fuel gas: A review

The present review paper highlighted on the recent progress of hot gas filtration, desulphurization and HCl removal in coal-derived fuel gas for combined cycle power generation (IGCC) or molten carbonate fuel cells (MCFC) technologies. As a critical process in the gasification system, hot gas filtration in the particulate control device (PCD) was introduced with enhanced understanding of equipment and operation, filter element and failsafe material properties, and gasification ash characteristics. The issues associated with the commercialization of hot gas filtration were also addressed, and some novel systems and methods were also discussed. The hot gas desulphurization in coal-derived fuel gas has concentrated on developing regenerable sorbents including the single and composite oxides of Zn, Fe, Cu, Mn and other species, and the reduction of metal oxides in the highly reducing atmosphere followed by vaporization of elements can be a problem for reactivity and regeneration. With regard to the removal of HCl, the studies have indicated sorbents prepared by pelletizing the powders of naturally available alkali metal and alkali earth metal substances can rapidly react with HCl vapor and reduce the HCl vapor concentration to less than 1 ppmv, and some sorbents lab-made have very high chlorine capacity. The sorbents based hot gas cleaning also has some challenges. Kinetics studies showed that unreacted shrinking core (USC) can be applied to the modeling of H₂S and HCl removal by sorbents at high temperature, and the surface chemical reaction and reactant diffusion by product layers between solid sorbents and gases were very important mechanisms. The paper also proposed and discussed a rational concept for the simultaneous removal of multiple contaminants including ash, H₂S and HCl, which will offer a possible cost reduction by two or more processes in a single vessel for hot gas cleaning.     

Microbial removal of sulfur dioxide from a gas stream

A study of the feasibility of utilizing the Thiobacillus ferrooxidans or Desulfovibrio desulfuricans bacterium for microbial removal of sulfur dioxide from flue gases has been carried out. Sulfur dioxide may be readily reduced to H₂S by contact with sulfate-reducing microorganisms in which Desulfovibrio desulfuricans were dominant in the first stage. The H₂S was then oxidized to sulfur by the ferric sulfate in a second stage where ferrous ions were regenerated. These results were compared to microbial oxidation of SO₂ from flue gases to sulfate by Thiobacillus ferrooxidans. The mechanisms for the reduction of SO₂ to H₂S in the presence of Desulfovibrio desulfuricans and the oxidation of SO₂ to H₂SO₄ in the presence of ferric sulfate and Thiobacillus ferrooxidans are discussed. Sulfuric acid or gypsum CaSO₄ · 2H₂O are byproducts from microbial flue gas desulfurization.     

Catalytic reforming of model tar compounds from hot coke oven gas with low steam/carbon ratio over Ni/MgO-Al2O3 catalysts

The catalytic reforming of toluene and naphthalene was performed to investigate the possibility for directly converting tar components from hot coke oven gas (COG) with lower steam/carbon (S/C) molar ratios to light fuel gases. The NiO/MgO-Al₂O₃ catalysts reduced exhibited excellent catalytic activity, stability and sulphur tolerance. The effects of various reaction conditions and S/C ratios on the catalytic performance were investigated in detail. Toluene and naphthalene were completely converted into small gas molecules at 700-800 °C and S/C = 0.28. An appropriate amount of steam benefited the methanation reaction of CO and H₂. The effects of N₂, CH₄ or CO in COG were also discussed. Relative to N₂, CO contributed to the conversion of toluene and the formation of CH₄, but the opposite was true for CH₄. The sulphur tolerance was tested by adding H₂S in the feed gas. The reaction results were explained by a water cycle mechanism.     

焦炉煤气管道沉积物的在线清洗

分析了焦炉煤气管道沉积物的成因与组成,采用化学药剂溶解和高温氨水清洗相结合的方法进行在线清理后,煤气管道内的沉积物得到有效清除,初冷器后至风机前煤气管道阻力由3 000Pa降至800Pa以下,焦炉装煤冒烟情况得以改善,风机后煤气焦油尘恢复正常,清洗过程安全无隐患。     

Investigation into the removal of sulfur from tire derived fuel by pyrolysis

There is growing interest in the use of scrap tires as both a fuel and a feed material for petroleum feedstocks due to their abundance and their chemical composition. However, the sulfur content of scrap tires is a potential obstacle to scrap tires utilization as a fuel. In this paper, the partitioning of sulfur was investigated from the two major pyrolytic products from passenger car tires, liquid oils and solid chars, and the potential of producing a low sulfur char for fuel applications. The removal of sulfur during tire pyrolysis offers the greatest potential for the separation of sulfur products from the evolved gases and vapors. The influences of heating rate and pyrolysis temperature were investigated from 325 to 1000 °C, a range where substantial devolatilization occurs. The pyrolysis char and derived oil were analyzed for sulfur, and compared to the original parent sulfur content in tire derived fuel (TDF) samples. The results of sulfur determination verify that the overall desulfurization from the pyrolysis reaction is essentially unaffected by the heating rate but is affected by the ultimate pyrolysis temperature.     

旧煤气管线改作天然气管线前清洗的重要性

论述了旧煤气管线改作输送天然气管线前,清除管线内壁焦油类沉积物及锈蚀产物的必要性,通过测定碳钢在四氢噻吩(THT)-石油醚溶液中的腐蚀性能,揭示残存的焦油能吸收添加在天然气中的THT,造成THT在管线输送过程中的额外损耗,并与此同时对送气管线构成一定的腐蚀.采用腐蚀挂片试验与XPS表面成分分析发现,在锈蚀的碳钢表面总伴有大量的含硫化合物吸附富集,吸附与锈蚀共存,二者是相互促进的关系.碳钢管线内壁发生腐蚀,也会引起THT的额外消耗,对清除旧煤气管线内壁的焦油和铁锈,提出了建议.     

生物质裂解气中焦油转化催化剂的研究现状

生物质裂解气中焦油的存在严重影响了燃气的热值和后续流程，因此焦油转化对生物质裂解制取合成气有着重要的意义，介绍了用于生物质裂解气中的焦油转化的催化剂体系，以及国内外在此领域的研究成果，展望了焦油转化催化剂的发展方向以及急需解决的问题。     

Tackling the problem of sulfur poisoning of perovskite catalysts for natural gas combustion

LaMn_0.5Mg_0.5O₃y MgO and LaCr_0.5-xMn_xMg_0.5O₃.y MgO catalysts (x=0-0.25, y=0-17) were prepared, characterized (XRD, BET, SEM-EDS, TEM, FTIR, chemical and atomic absorption analyses), tested for high-temperature methane combustion and aged in presence of SO₂ to investigate sulfur effect on catalytic activity. Different roles of manganese and chromium in the perovskite structure have been assessed: (i) manganese improves the activity of catalysts in the fresh state, whereas chromium worsens it; (ii) owing to its basic nature, manganese makes perovskites more prone to adsorb SO₂ and so less resistant to sulfur poisoning, whereas chromium, owing to its acidic nature, has opposite effects; (iii) the partial solubility of chromium oxide in basic media renders Cr-catalyst regeneration by NH₃ leaching less effective. MgO promotes catalytic activity of fresh LaCr_0.5Mg_0.5O₃.y MgO catalysts and slows down sulfur poisoning of LaMn_0.5Mg_0.5O₃.y MgO and LaCr_0.25Mn_0.25Mg_0.5O₃.17 MgO catalysts only.     

采用有机盐─石膏脱硫剂的烟气脱硫新工艺

介绍一种利用有机羧酸盐作为吸收剂、以熟石灰作还原剂的烟气脱硫系统，在日本投入生产运行，其脱硫效率达９０％以上。     

Partial oxidation of methane to synthesis gas over iridium–nickel bimetallic catalysts

Partial oxidation of methane to synthesis gas was carried out using supported iridium–nickel bimetallic catalysts, in order to reduce loading levels of iridium and nickel, and to avoid carbon deposition on nickel-based catalysts by adding iridium. The performance of supported iridium–nickel bimetallic catalysts in synthesis gas formation depended strongly upon the support materials. La₂O₃ gave the best performance among the support materials tested. Ir(0.25 wt%)–Ni(0.5 wt%)/La₂O₃ afforded 36% conversion of methane (CH₄/O₂=5) to give CO and H₂ with the selectivities of above 90% at 800°C, and those at 600°C were 25.3% conversion of methane and CO and H₂ selectivities of about 80%, respectively. Reduced monometallic Ir(0.25 wt%)/La₂O₃ and Ni(0.5 wt%)/La₂O₃ catalysts did not produce synthesis gas at 600°C. A higher conversion of methane was obtained by synergistic effects. The product concentrations of CO, H₂, and CO₂, and CH₄ conversion were maintained in high values, even increasing the space velocity of feed gas over Ir–Ni/La₂O₃ catalyst, indicating that rapid reaction takes place. As a by-product, a small amount of carbon deposition was observed, but carbon formation decreased with increasing the space velocity. On the other hand, with reduced monometallic Ni(10 wt%)/La₂O₃ catalyst, yield of synthesis gas and carbon decreased with increasing the space velocity.