蒙古国巴嘎诺尔(Baganuur)褐煤水蒸气气化制富氢合成气及其固有矿物质的催化作用
Hydrogen rich syngas production by the steam gasification of Mongolia Baganuur lignite and the catalytic effect of inherent minerals
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摘要: 利用固定床气化-色谱联用装置,考察了蒙古国巴嘎诺尔(Baganuur)褐煤的水蒸气气化反应性能,研究对比了巴嘎诺尔褐煤原煤BN-R、盐酸洗煤BN-HCl、氨水洗煤BN-NH4OH、先酸洗后碱处理煤BN-HCl-NaOH及原煤和盐酸洗煤热解预处理煤样BN-R-Char与BN-HCl-Char在水蒸气气化过程中气态产物H2、CO和CO2的生成规律.研究结果表明,上述煤样的水蒸气气化过程中H2、CO和CO2的生成速率存在明显差异,与盐酸洗煤样相比,BN-R、BN-HCl-NaOH及BN-R-Char比对应矿物质脱除煤样的水蒸气气化速率高,充分说明巴嘎诺尔褐煤中某些固有矿物质对其水蒸气气化反应具有显著的催化作用,显著提高了其气化反应速率,使起始气化温度和气化反应主体温度均降低100 ℃以上,在提高H2和CO2生成量同时,还降低了CO生成量,制得了高H2/CO(物质的量比)的合成气.用盐酸脱除矿物质所得BN-HCl同BN-HCl-Char的水蒸气气化性能相似.与BN-R相比,BN-HCl与BN-HCl-Char水蒸气气化反应性明显下降,说明对巴嘎诺尔褐煤水蒸气气化起催化作用的矿物质成分在盐酸洗脱的矿物质中.经过分析,发现矿物质对巴嘎诺尔褐煤水蒸气气化反应的催化作用,主要是通过提高水煤气变换反应速率实现的.最后,结合文献报道,提出了巴嘎诺尔褐煤水蒸气气化反应过程中矿物质的原位催化机理.Abstract: The temperature programmed steam gasification (TPSG) of lignite from Baganuur, Mongolia was studied in a micro fixed-bed reactor with chromatography. The formation rate of H2,CO and CO2 during the TPSG were examined using the lignite samples pretreated by washing with HCl and NH4OH solution or NaOH solution following the washing by HCl solution. All the samples were pyrolyzed at 650 ℃. The results show that a significant difference in the formation rate of gas components is presented for the tested lignite samples. The inherent minerals in the Baganuur lignite can accelerate the generation rate of H2 and CO2, but simultaneously reduce the generation rate of CO, which could manufacture a high H2/CO mol ratio syngas. Also, some inherent minerals in the Baganuur lignite can remarkably enhance the steam gasification rate, which results in an drop of initial steam gasification reaction temperature by over 100 ℃. It is speculated that the enhanced steam gasification reaction of Baganuur lignite could be attributed to the effect of some inherent minerals on the water-gas shift reaction. Finally, the possible in-situ catalytic mechanism of inherent minerals in Baganuur lignite to the steam gasification reaction is discussed.