Catalytic upgrading of gaseous tar from coal pyrolysis over Mo and Ni-modified HZSM-5
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摘要: 考察了Mo和Ni改性的HZSM-5催化剂对煤热解焦油的改质性能, 分析了催化改质前后焦油中轻质芳烃分布的变化规律。结果表明, 经HZSM-5催化剂褐煤(XM) 热解轻质芳烃总量的增加率为220%, 这与煤热解产物在HZSM-5催化剂中发生烯烃和烷烃的芳构化以及酚羟基脱除等作用有关。负载活性金属Mo和Ni后, 可以有效促进轻质芳烃的生成; Ni对焦油中带脂肪侧链化合物具有更强的裂解作用, 而Mo则有利于带侧链化合物如甲苯和二甲苯的形成。焦煤(FX) 热解过程中轻质芳烃的释放量分别是XM煤和年轻烟煤(PS) 的2.2和2.4倍。经催化改质后, XM煤产物中轻质芳烃产率明显大于PS煤, 并接近FX煤; 这主要是因为XM煤结构中含有较多的含氧官能团和脂肪结构, 在HZSM-5作用下可催化形成轻质芳烃。Abstract: The distributions of light aromatic hydrocarbons in the gaseous tar were investigated upon upgrading over Mo and Ni-modified HZSM-5 catalysts during coal pyrolysis. The results show that the yield of light aromatic hydrocarbon from lignite (XM) pyrolysis is increased by 220% after the cracking of gaseous tar over HZSM-5 zeolite, due to the aromatization of olefins or alkanes and the dehydroxylation of phenols. The loading of Mo and Ni on HZSM-5 is able to enhance the formation of light aromatic hydrocarbons; Ni can obviously promote the side chain cracking, whereas Mo is more effective for the formation of aromatic compounds with side chains such as toluene and xylene. Without catalysts, the yield of light aromatic hydrocarbons from coking coal (FX) pyrolysis is about 2.2 and 2.4 times higher than that from XM and bituminous coal (PS) pyrolysis, respectively. By using catalysts, however, the yield of light aromatic hydrocarbons from XM pyrolysis is obviously higher than that from PS pyrolysis and close to that from FX pyrolysis, as XM is provided with abundant oxygen containing functional group and aliphatic structure that can be transformed to light aromatic hydrocarbons over the HZSM-5 catalysts.
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Key words:
- coal pyrolysis /
- gaseous tar /
- catalytic upgrading /
- light aromatic hydrocarbons
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图 1 Mo和Ni改性HZSM-5催化剂的XRD谱图
Figure 1 XRD patterns of Mo and Ni-modified HZSM-5
a: HZSM-5; b: 5%Mo/HZSM-5; c: 10%Mo/HZSM-5; d: 5%Ni/HZSM-5; e: 10%Ni/HZSM-5
图 2 经催化后XM煤热解产物中BTEXN总量增加率
Figure 2 Increasing rate of the content of BTEXN (benzene, toluene, ethylbenzene, xylenes and naphthalene) upon catalytic upgrading of gaseous tar during XM pyrolysis
图 5 700 ℃下不同变质程度煤热解产物中BTEXN的生成量
Figure 5 Release amounts of BTEXN during pyrolysis of different rank coals at 700 ℃
图 6 700 ℃下不同变质程度煤热解焦油经5%Mo/HZSM-5和5%Ni/HZSM-5催化后BTEXN的释放量
Figure 6 Release amounts of BTEXN after upgrading of gaseous tar over 5%Mo/HZSM-5 and 5%Ni/HZSM-5 catalysts during pyrolysis of different rank coals at 700 ℃
图 7 700 ℃下XM煤热解焦油经5%Mo/HZSM-5和5%Ni/HZSM-5催化后BTEXN各组分的释放量
Figure 7 Release amounts of BTEXN after upgrading of gaseous tar over 5%Mo/HZSM-5 and 5%Ni/HZSM-5 catalysts during pyrolysis of XM at 700 ℃
图 8 700 ℃下PS煤热解焦油经5%Mo/HZSM-5和5%Ni/HZSM-5催化后BTEXN各组分的释放量
Figure 8 Release amounts of BTEXN after upgrading of gaseous tar over 5%Mo/HZSM-5 and 5%Ni/HZSM-5 catalysts during pyrolysis of PS at 700 ℃
图 9 700 ℃下FX煤热解焦油经5%Mo/HZSM-5和5%Ni/HZSM-5催化后BTEXN各组分的释放量
Figure 9 Release amount of BTEXN after upgrading of gaseous tar over 5%Mo/HZSM-5 and 5%Ni/HZSM-5 catalysts during pyrolysis of FX at 700 ℃
表 1 煤样的工业分析和元素分析
Table 1 Proximate and ultimate analyses of coal samples
Sample Proximate analysis w/% Ultimate analysis wdaf /% Mad Ad Vdaf C H O* N S Lignite (XM) 29.8 8.85 45.9 74.9 3.45 17.5 1.20 2.97 Bituminous coal (PS) 2.23 18.3 37.2 80.4 5.20 12.0 1.38 1.06 Coking coal (FX) 0.52 7.55 26.4 86.5 3.98 6.64 1.20 1.72 *: by difference 
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表 2 催化剂的孔结构性质
Table 2 Textural property of various catalysts
Catalyst ABET/(m2·g-1) Micropore volume v/(cm3·g-1) Pore diameter d/nm HZSM-5 264 0.115 0.59 5%Mo/HZSM-5 236 0.102 0.60 10%Mo/HZSM-5 202 0.088 0.60 5%Ni/HZSM-5 228 0.094 0.61 10%Ni/HZSM-5 218 0.095 0.57
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