Study on component enrichment and storage stability of bio-oils obtained from fractional condensation
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摘要: 利用GC-MS分别检测分级冷凝装置和常规冷凝装置制备的核桃壳生物油，对比常规冷凝生物油与分级冷凝多品级生物油有机组分的相对峰面积，发现分级冷凝对组分富集有较大影响，其中，乙酸在第四级生物油内相对峰面积从5.38%上升至9.44%；愈创木酚在第二级内从3.46%上升至6.23%；紫丁香醇在第一级内从1.48%上升至4.44%；异丁香酚在第一级内从5.52%上升至17.84%。经过75 d、15℃恒温恒湿储存后分级冷凝生物油水分增加，分别增加了1.58%、1.88%、1.80%、2.43%；脂肪类有机物峰面积减小；酚类有机物峰面积增大。第一、二级生物油内小分子有机物含量较少，老化反应强度较低；第三、四级生物油内小分子有机物含量较多，老化反应强度较高。根据GC-MS检测结果将有机物分类，统计各类有机物在储存前后的含量变化，分析储存过程中各类有机物发生的老化反应种类以及反应强度。Abstract: The bio-oils from ordinary condensation and from fractional condensation were analyzed by GC-MS. Comparing the relative peak areas of these, the result shows that the fractional condensation has an obvious effect on component enrichment. The acetic acid in the 4th step condensation increases from 5.38% to 9.44%, the guaiacol in the 2nd step condensation increases from 3.46% to 6.23%, and the sringol and isoeugenol in the 1st step condensation increase from 1.48% to 4.44% and from 5.52% to 17.84%, respectively. After 75 days' storage stability experiment on the physicochemical properties of multi-fraction bio-oils obtained from fractional condensation in a 15℃ constant temperature and humidity box, the water content of the fractional bio-oils increases by 1.58%, 1.88%, 1.80% and 2.43%, respectively. Besides, the acids, aldehydes, ketones and alcohols decrease after storage because light components are consumed by chemical reaction. The relative peak areas of phenols increases slightly. It suggests that the chemical reactions in the bio-oil from 1st and 2nd step condensations can be negligible, while the chemical reactions in the bio-oil from 3rd and 4th step condensations are active. Organics in bio-oils can be classified by the analysis of GC-MS both before and after storage for analyzing the kinds and intensities of the chemical reactions in bio-oils.
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Key words:
- bio-oils /
- fractional condensation /
- component enrichment /
- component analysis /
- storage stability
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图 1 生物质流化床热解与分级冷凝装置示意图
Figure 1 A fluidized bed pyrolysis apparatus with four fractional condensers
1: hopper; 2: fluidized bed; 3: carbon collector; 4: cyclone separator; 5: spray tank; 6: thermostat; 7: cooling pond; 8: filter; 9: compressor; 10: electric heater room; 11: electric heating sleeve Ⅰ: the 1st step condensation; Ⅱ: the 2nd step condensation; Ⅲ: the 3rd step condensation; Ⅳ: the 4th step condensation
图 3 储存前后各级生物油的总离子图
Figure 3 Bio-oils' chromatograms before and after storage
(a): 0 d bio-oils' chromatograms; (b): 75 d bio-oils' chromatograms
图 4 储存前后酸、酮、呋喃类有机物峰面积变化
Figure 4 Acids, ketones, furans variation before and after storage
A: acids; B: ketones; C: furans
图 5 储存前后酚类有机物峰面积变化
Figure 5 Phenols variation before and after storage
D: phenols; E: guaiacols; F: syringol
表 1 核桃壳的工业分析和元素分析
Table 1 Proximate and ultimate analyses of walnut shells
Proximate analysis
war/%Moisture Volatile Ash Fixed carbon* 3.73 74.32 20.98 0.97 Ultimate analysis
wdaf/%C H O* N S 52.62 5.67 41.26 0.34 0.11 *: by difference 
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表 2 常规冷凝与分级冷凝生物油有机组分相对峰面积
Table 2 Relative peak areas of organics from ordinary and fractional condensation
Main indentified compound Boiling point t/℃ Relative peak area w/% ordinary BIO1 BIO2 BIO3 BIO4 Methylcyclopentenolone 74.0 0.65 0.54 0.99 1.32 1.02 2, 5-dimethylfuran 93.0 1.28 1.26 2.65 3.51 2.78 1, 1-diethoxyethane 102.7 0.96 - - - - Acetic acid glacial 117.9 5.38 5.66 5.60 7.87 9.44 Hydroxypropanone 145.5 1.26 0.57 0.64 0.48 0.70 2, 5-dimethoxytetrahydrofuran 146.0 0.16 - - 0.32 - 3-methyl-1-pentanol 153.0 - - - 0.88 0.64 2-ethylbutyl acetate 162.0 - - 0.41 - - 1-acetoxy-2-butanone 171.0 - 0.35 0.30 0.32 0.54 3-methylanisole 175.0 - - - 0.31 - Benzaldehyde 179.0 - - - 0.54 0.35 Phenol 182.0 1.67 1.07 1.03 1.77 2.12 Ethylene glycol diacetate 186.5 - - - 0.82 0.80 5-methyl furfural 187.0 - - 0.34 0.38 0.61 2-furaldehydediethylacetal 190.0 - - 0.40 0.62 0.57 Salicylaldehyde 197.0 - 0.66 0.68 1.38 1.13 2-methyl benzofuran 197.0 - - - 0.47 0.31 M-cresol 203.0 2.41 0.98 0.97 2.16 2.17 Guaiacol 205.0 3.46 5.45 6.23 5.32 5.07 3-methyl-1H-indene 206.0 0.35 - - 0.46 - Naphthalene 218.0 0.92 - - 1.72 1.42 4-ethylphenol 218.5 0.62 - - - - 4-vinylguaiacol 224.0 - 4.92 4.40 1.41 3.01 2, 3-dimethyl phenol 227.0 1.92 0.78 0.77 2.05 1.88 1-ethylidene-1H-indene 229.0 - - - - 0.37 2, 4, 5-trimethylphenol 232.0 - - - 0.43 0.35 3-ethyl-5-methylphenol 233.0 0.59 - - 1.65 1.24 4-ethyl guaiacol 235.0 1.65 3.97 3.77 2.82 2.96 Carvacrol 237.0 0.40 - - 0.46 0.44 Catechol 245.0 4.98 - - 1.94 2.69 Eugenol 254.0 1.35 - - - - Syringol 261.0 1.48 4.44 4.19 3.18 3.03 Isoeugenol 266.0 5.52 17.84 14.44 9.25 10.17 3-tert-butyl-4-hydroxyanisole 269.0 - 2.06 1.83 0.62 1.51 4-hydroxy-3-methoxyphenylac etone 305.0 0.94 - 0.73 0.64 0.58 Palmitic acid 351.5 0.75 - - 0.53 0.44 Oleic acid 360.0 7.29 5.41 1.00 4.68 3.73 4-hydroxy-3-methoxycinnamylic alcohol 393.0 - - - 0.30 0.31 2, 4-dimethoxytoluene 115(30 mmHg) - 0.35 - - - 1, 3-cyclopentanediol 82.5(0.1 mmHg) - - - 0.39 - 4-allyl-2, 6-dimethoxyphenol 168(11 mmHg) 1.71 6.30 4.77 1.94 3.68 Dihydroeugenol 125.5(14 mmHg) - 1.15 1.07 0.62 0.57 4-hydroxy-3-methylacetophenone 175.0(1 mmHg) 1.67 1.07 1.00 0.88 0.95 Syringaldehyde 192.5(14 mmHg) - 0.59 0.70 0.71 0.83 Methyl oleate 218(20 mmHg) 8.00 - 1.02 1.18 - 4-methyl guaiacol * 3.27 6.95 7.38 4.46 4.55 1-(4-methoxyphenyl)-1-propanol * - 0.34 0.32 - - 5-O-methylhierochind * - 0.58 - - - 1-(2, 4, 6-trihydroxy-3-methylphenyl)-1-butanone * - 0.37 0.40 0.38 0.50 1-ethyl-2-(2-ethylphenyl)benzene * - 0.34 0.36 0.31 0.42 1, 2-dipalmitoyl-SN-glycerol * 0.71 0.73 0.46 - - 3, 5-dimethoxycinnamic acid * - 0.51 0.83 0.61 0.38 Methyl elaidate * - 0.41 - - - Acetoxy-2-propanone * 0.34 - 0.66 - - (E)-tetradec-9-en-1-ol * - - - 0.37 - note：boiling point in the table from ichemistry, *: unknown boiling point; -: relative peak area < 0.3%
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表 3 生物油水分随储存时间的变化
Table 3 Water content variation of bio-oils with storage time
Content w/% 0 d 5 d 15 d 35 d 75 d BIO1 9.72 9.98 10.45 10.73 11.29 BIO2 13.49 13.77 14.55 14.51 15.37 BIO3 21.85 21.93 22.39 22.95 23.65 BIO4 13.21 13.29 13.99 14.67 15.65
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表 4 生物油内醛、醇、酯类相对峰面积分布
Table 4 Relative peak area of aldehydes, alcohols, esters
Species Content w/% BIO3-0 BIO3-75 BIO4-0 BIO4-75 Aldehyde 1.55 - - - Alcohol 0.88 - 0.64 - Ester 2.00 1.41 1.65 - -: relative peak area < 0.5%
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