Experimental study on bio-oil from catalytic pyrolysis on Fe modified HZSM-5
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摘要: 通过离子交换法制备含2%Fe (质量分数) 的HZSM-5催化剂, 采用X射线衍射仪(XRD)、激光粒度分析仪以及比表面积及孔径分析仪对催化剂进行表征, 并在550 ℃下进行木屑的催化热解实验。对无催化剂和不同比例催化剂条件下得到的生物油进行GC-MS分析, 结果表明, 在Fe负载的HZSM-5作用下, 生物油产率明显升高(最大增幅7%), 轻质组分产率明显升高, 重质组分产率略微升高。同时, 轻质组分中的酮类、呋喃等含氧化合物含量降低, 酚类、酸含量升高; 重质组分中的酮类、呋喃类等含氧化合物含量明显降低, 酚类、萘类含量明显增多。Fe负载的HZSM-5催化剂对木屑的热解反应有较好的催化效果, 加强了对热解初始蒸汽的择形修饰, 从而抑制了生物质三组分木质素初始热解产物中的醌类等容易一次或二次结焦物质的生成, 孔道结构对蒸汽的二次反应被抑制, 产物向较小分子的轻质产物上富集。Abstract: The 2% Fe modified HZSM-5 zeolite catalysts were prepared by ion-exchange and characterized by laser particle size analyzer, specific surface area and pore size analyzer, and X-ray diffraction (XRD) to investigate the pore and surface properties. The catalytic pyrolysis of wood was carried out at 550 ℃ to get the maximum oil yield. After pyrolysis, the bio-oil was separated to the lighter (upper layer) and heavier component (bottom layer). The results indicate that with Fe modified HZSM-5 catalysts, the bio-oil yield increases significantly (maximum 7%) the same as that of the lighter one, while the heavier one is nearly constant. Ketones and furans in the lighter oil decreases, while acids and phenols increase significantly; in the heavier oil, ketones and furans decreased dramatically, phenols and naphthalenes increase significantly. The Fe modified HZSM-5 catalysts play an important role in pyrolysis of wood dusts, and have a critical influence on oil yield because the modified catalysts promote the shape-selective modifying of the initial pyrolysis steam and inhibit the secondary coking reaction of steam. The product tends to much lighter bio-oil component and lower oxygen content.
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Key words:
- Fe modified /
- HZSM-5 /
- catalytic pyrolysis /
- bio-oil
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表 1 木屑的工业分析与元素分析
Table 1 Proximate and ultimate analyses of sawdust
Proximate analysis wad/% Ultimate analysis wad/% M V A FC C H N S O* 4.44 85.47 1.25 8.84 52.49 5.70 0.96 0.57 34.59 =*: by difference 表 2 催化剂的孔隙结构参数
Table 2 Pore structure parameters of catalysts
Type BET surface area A/(m2·g-1) Pore volume v/(cm3·g-1) Pore size d/nm HZSM-5 336.21 0.192 3 2.52 Fe/HZSM-5 315.68 0.1852 2.50 表 3 Fe负载上层轻质组分GC-MS产物分布
Table 3 Composition of the upper light oil through Fe/HZSM-5 catalyst by GC-MS analysis
Name Non-catalyst
peak area /%(0.3g Fe/HZSM-5)
peak area /%(0.6g Fe/HZSM-5)
peak area /%(0.9g Fe/HZSM-5)
peak area /%Acetic acid 32.3 39.9 41.98 45.84 2-propanone, 1-hydroxy- 12.48 13.38 13.7 16.28 Propanoic acid 3.76 3.7 3.84 2.67 2-propen-1-ol 1.23 1-propanol 3.15 1, 2-ethanediol, diacetate 2.19 Furfural 5.38 5.34 3-furanol, tetrahydro- 1.41 2-methoxytetrahydrofuran 1.23 Furan, tetrahydro-2, 5-dimethoxy- 0.45 1-hydroxy-2-butanone 3.42 3.86 3.22 Cyclopentanone 5.53 4.71 2-cyclopenten-1-one 5.93 4.86 2-cyclopenten-1-one, 2-methyl- 2.08 1.02 0.94 0.9 Butanoic acid 1.92 1.44 Butyrolactone 1.74 1.69 1.44 0.91 2, 3-butanedione 1.78 2-cyclopenten-1-one, 2-hydroxy-3-methyl- 2.67 1, 2-cyclopentanedione, 3-methyl- 1.88 1.75 0.91 2-cyclopenten-1-one, 2, 3-dimethyl- 1.11 Piperidine, 1-methyl- 0.84 Phenol 1.03 0.8 0.85 Phenol, 2-methyl- 1.6 1.11 0.94 1.53 Phenol, 2-methoxy- 1.71 1.17 Phenol, 4-methyl- 1.53 0.69 Phenol, 2, 4-dimethyl- 0.58 Phenol, 2-methoxy-4-methyl- 2.23 1, 6;2, 3-dianhydro-4-O-acetyl-. 2.18 1.62 beta.-d-gulopyranose 1, 2-benzenediol 5.58 6.79 8.53 9.62 1, 2-benzenediol, 3-methyl- 1.28 1, 2-benzenediol, 4-methyl- 1.63 表 4 Fe负载下层重质组分GC-MS产物的分布
Table 4 Composition of the lower heavy oil through Fe/HZSM-5 catalyst by GC-MS analysis
Name Non-catalyst
peak area /%(0.3 g Fe/HZSM-5)
peak area /%(0.6 g Fe/HZSM-5)
peak area /%(0.9 g Fe/HZSM-5)
peak area /%Acetic acid 18.38 8.52 9.08 13.73 2-propanone, 1-hydroxy- 3.31 0.98 1.08 2.02 Propanoic acid 3.3 0.67 2-pentanone, 4-hydroxy-4-methyl- 1.17 Formic acid phenyl ester 1.77 3-hexyne, 2-methyl- 0.78 2, 4-hexadiene, 2, 3-dimethyl- 0.58 Furfural 5.31 4.28 3.25 1-hydroxy-2-butanone 0.54 Cyclopentanone 2.68 1.31 0.75 2-cyclopenten-1-one 1.9 3.63 1.69 2-cyclopenten-1-one, 2-methyl- 1.35 1.04 0.94 2-cyclopenten-1-one, 3-methyl- 1.93 0.9 1.58 Butyrolactone 0.98 0.83 1, 3-butadiene, 2, 3-dimethyl- 0.41 1, 2-cyclopentanedione, 3-methyl- 0.66 0.81 2-cyclopenten-1-one, 2, 3-dimethyl- 2.58 2.33 0.74 2-cyclopenten-1-one, 3-ethyl-2-hydroxy- 0.14 Toluene 0.5 0.52 0.73 p-xylene 0.63 1.04 0.88 Phenol 1.6 3.07 1.67 Phenol, 2-methyl- 3.68 3.42 3.21 4.26 Phenol, 2-methoxy- 4.98 3.1 7.46 Phenol, 4-methyl- 3.74 4.03 Phenol, 2, 3-dimethyl- 1.38 2.47 0.72 1.33 Phenol, 2, 4-dimethyl- 5.87 5.12 4 5.29 Phenol, 2, 5-dimethyl- 2.06 4.15 Phenol, 2, 4, 6-trimethyl- 1.17 6.04 1.98 Phenol, 2-ethyl- 2.46 1.77 1.98 Benzene, 1-ethyl-4-methoxy- 3.11 0.7 2.72 4.22 2-hydroxy-3-methylbenzaldehyde 0.79 1.27 Benzaldehyde, 4-(1-methylethyl)- 1.01 1, 2-benzenediol 2.88 1, 2-benzenediol, 3-methyl- 1.1 2.92 1, 3-benzenediol, 4, 5-dimethyl- 0.6 2.27 1, 3-benzenediol, 4-ethyl- 4.78 Phenol, 4-ethyl-2-methoxy- 1.76 3.57 5.39 Phenol, 2-ethyl-6-methyl- 3.48 1.28 1.52 Phenol, 2-methoxy-3-methyl- 1.53 Phenol, 2-methoxy-4-methyl- 1.48 1.3 3.04 Phenol, 2, 3, 5, 6-tetramethyl- 1.01 Thymol 0.79 0.75 Benzene, 1-methoxy-4-(1-methylethyl)- 0.38 Benzene, 1, 3, 5-triethyl- 0.99 Phenol, 4-(1-methylpropyl)- 1.39 Indene 3.87 Indane 0.21 0.31 1H-indene, 1, 3-dimethyl- 0.14 0.25 1H-indene, 1, 1-dimethyl- 0.13 1H-inden-5-ol, 2, 3-dihydro- 0.2 0.97 5-hydroxy-3-methyl-1-indanone 0.8 2-allylphenol 2.7 2.27 1.1 0.86 2-allyl-4-methylphenol 5.76 4.11 2.97 2.95 3-allyl-6-methoxyphenol 3.2 4.43 Naphthalene 1.47 2.36 3.16 1-naphthalenol, 2-methyl- 0.43 1.6 1.98 Naphthalene, 2-methyl- 1.6 1.74 4.6 Naphthalene, 2, 6-dimethyl- 0.69 1.47 Naphthalene, 2, 3, 6-trimethyl- 1.1 Naphthalene, 2, 6-bis (1, 1-dimethylethyl)- 1.08 2-methoxy-4-vinylphenol 4.96 3.39 Phenol, 2-methoxy-4-propyl- 2.26 1, 2-benzenediol, 4-methyl- 7.27 5.71 Butylated hydroxytoluene 2.28 Phenol, 2-methoxy-4-(1-propenyl)- 3.78 9.04 Phenol, 2-methoxy-3-(2-propenyl)- 1.85 2 2-methyl-6-propylphenol 2.63 3.18 0.76 2.02 Acetophenone, 4'-methoxy- 2 1.63 0.72 1.98 Bicyclo[4.2.0]octa-1, 3, 5-triene 1.45 -
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