不同气氛下煤连续热解产物的分配规律及产品品质分析

Analysis of product distribution and quality for continuous pyrolysis of coal in different atomspheres

  • 摘要: 在连续进出料的流化床中研究了热解温度为850 ℃时,含有O2、H2、CO、CO2、CH4的反应气氛对热解产物分配规律及产品组成的影响。采用Raman、BET等测试方法对不同热解气氛下制得半焦的品质进行了评价,结合热重分析了影响半焦反应活性的因素。结果表明,无O2气氛下,H2与CO2存在时降低了焦油产率,而CO与CH4促进了焦油的生成。CH4的裂解析碳使半焦产率上升。O2的加入使CO2、CO含量明显增加,半焦及焦油产率降低。N2中引入O2时,PAHs含量降低。CH4促进了烷基萘与苯类的生成,CO则抑制酚类裂解生成苯类。CO2的气化作用促进了微孔的生成,相应地,半焦的比表面积快速增加,半焦的反应活性也最高。CO歧化与CH4热裂解产生的析碳堵塞了部分孔道,降低了比表面积。H2与CH4所产生的氢自由基能渗透到半焦内部,引起半焦结构的缩聚,进而影响氧化反应活性。

     

    Abstract: The continuous coal pyrolysis at 850 ℃ in a fluidized bed reactor under atmospheres containing O2, H2, CO, CH4, N2 and CO2 were carried out. The char product was characterized using Raman, BET and TGA (for evaluating reactivity). The results show that without O2 in the atmosphere, adding H2 and CO2 lowers the pyrolysis tar yield which is conversely higher with raising the CO and CH4 contents in the atmosphere. The introduction of O2 promotes the formation of CO and CO2, and thus the yields of tar and char decrease. The char yield increases with the addition of CH4 into the pure N2 atmosphere, which is ascribed to the cracking of CH4. PAHs content decreases with the addition of O2 into N2 atmosphere. CH4 promotes the production of alkyl-substituted naphthalenes and benzenes. CO inhibits the cracking of phenols to form benzenes. CO2 facilitates the formation of new micropores or opening of the closed pores, producing the chars with high surface area and the corresponding highest oxidation reactivity. The carbon deposition via CO disproportionation and CH4 cracking in the presence of CO/CH4 blocks some pores and thus lowers the surface area and reactivity of the char. The char produced with the inclusion of H2 and CH4 results in a more condensed crystallite structure via hydrogen radicals penetration and thus lowers the oxidation reactivity.

     

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