Effects of diphenylethene on products produced during cornstalk cellulose liquefaction in supercritical ethanol
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摘要: 以1，1-二苯乙烯（DPE）为阻聚剂，采用高压反应釜对玉米秸秆纤维素进行超临界乙醇液化，探究DPE浓度（用量）和反应温度对纤维素裂解碎片转化成液化产物的影响。结果表明，DPE浓度增加，挥发分收率降低了25.4%，生物油收率增加了19.9%，收率最高达39.8%，纤维素转化率有所下降；反应温度升高，纤维素转化率迅速增加到85.5%，挥发分也急剧升高，生物油收率最高为34.6%。GC-MS结果显示，生物油主要包括酮类、酯类、烃类等平台化合物以及较多的联苯化合物。DPE浓度过高，结合大量的纤维素裂解片段（乙基、羟基、甲基、氢等）形成联苯类化合物产生较强的空间位阻效应，使得纤维素裂解及活性片段转化成平台化合物的反应受到抑制，两者之间是一个竞争过程；温度升高，乙醇自由基活性增强，其对纤维素裂解的促进作用逐渐超过DPE对纤维素裂解的抑制作用，平台化合物收率有所升高。Abstract: With 1, 1-diphenylethene (DPE) as the polymerization inhibitor, the effects of DPE concentration (dosage) and reaction temperature on the active fragments transforming to liquefaction products during cellulose liquefaction in supercritical ethanol were investigated using an autoclave. As the DPE concentration increases, the yield of volatile compounds decreases by 25.4%, while the yield of bio-oil increases to 39.8%, and the cellulose conversion rate decreases gradually. With the increasing of reaction temperature, the cellulose conversion rate reaches to 85.5% sharply and the volatile compounds also increases fastly, but the maximum bio-oil yield drops to 34.6%. GC-MS analysis shows that ketones, esters, alkanes, alcohols, acids and the DPE derivatives are dominant platform chemicals in the bio-oil. A lot of active fragments (such as CH3CH2-, HO-, H-, CH3-, etc.) produced from cellulose pyrolysis in supercritical ethanol are trapped by a higher concentration of DPE to form DPE derivatives, which has a strong steric effect on the fragments transforming to platform chemicals. With the increasing of temperature, the enhanced pyrolysis of cellulose by ethanol radicals is more significant in comparison with the inhibition of DPE, resulting in an improvement in the content of platform chemicals.
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Key words:
- diphenylethene /
- cornstalk cellulose /
- supercritical ethanol /
- liquefaction /
- platform chemicals
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图 1 纤维素超临界乙醇/DPE液化实验流程示意图
Figure 1 Procedures for the liquefaction of cellulose in supercritical ethanol with DPE
图 2 不同DPE用量下纤维素超临界乙醇液化产物收率及纤维素转化率
Figure 2 Products yield and conversion rate of cellulose liquefaction in 100mL ethanol with various DPE dosages at 280℃ under 7.5-7.7MPa for 60min
图 3 不同反应温度下纤维素超临界乙醇液化产物收率及纤维素转化率
Figure 3 Products yield and conversion rate of cellulose liquefaction in 100mL ethanol under various temperatures with 0.3g DPE under 6.4-10.2MPa for 60min
图 4 不同DPE用量纤维素液化生物油中主要化合物分布
Figure 4 Distribution of compounds in BO obtained from cellulose liquefaction in 100mL ethanol with various DPE dosages at 280℃ under 7.5-7.7MPa for 60min
图 5 不同温度纤维素液化生物油中主要化合物分布
Figure 5 Distribution of dominant compounds in BO obtained from cellulose liquefaction in 100mL ethanol under various temperatures with 0.3g DPE under 6.4-10.2MPa for 60min
图 6 路径Ⅰ和路径Ⅱ：纤维素通过LGO和逆醇醛缩合裂解生成酮类、酯类等化合物
Figure 6 PathⅠand pathⅡ: cellulose pyrolysis to ketones and esters through LGO and reverse aldol condensation
图 7 路径Ⅲ：脂肪酮、醇、酯类及环戊酮类生成路径示意图
Figure 7 PathⅢ: aliphatic ketones, alcohols, esters and cyclopentanones formation route
(R=-OH, -H, -CH3, CH3CO-, CH3CH2-, etc)
图 9 路径Ⅴ：脂肪酮类、环酮类、芳香酮类及酯类生成路径示意图
Figure 9 PathⅣ: aliphatic ketones, cyclic ketones, aromatic ketones and esters formation route
表 1 不同DPE用量下纤维素液化生物油GC-MS分析主要组分
Table 1 GC-MS results of BO obtained from cellulose liquefaction under various of DPE dosages
RT t/min Name of compounds Formula Alkanes 12.85 octane, 5-ethyl-2-methyl- C11H24 18.45 tetradecane, 5-methyl- C15H32 18.88 dodecane, 4, 6-dimethyl- C14H30 19.12 nonane, 3-methyl-5-propyl- C13H28 20.84 heptane, 1, 1-diethoxy- C11H24O2 21.82 heptadecane C17H36 22.03 diphenylmethane C13H12 22.40 hexadecane C16H34 23.39 eicosane C22H46 23.62 hexadecane, 2, 6, 10, 14-tetramethyl- C20H42 24.49 pentadecane, 2, 6, 10-trimethyl- C19H40 Ketones 5.07 2-pentanone, 4-hydroxy- C5H10O2 5.71 2-cyclopenten-1-one C5H6O 5.77 2-pentanone, 4-hydroxy-4-methyl- C5H10O2 19.04 2-hydroxy-iso-butyrophenone C10H12O2 20.65 3(2H)-furanone, dihydro-5-isopropyl- C7H12O2 24.45 benzophenone C13H10O Esters 5.36 pentanoic acid, 3-hydroxy-4-methyl-, methyl ester C7H14O3 7.88 2-propenoic acid, butyl ester C7H12O2 18.29 butanoic acid, 4-phenoxy-, ethyl ester C12H16O3 26.32 oxalic acid, 6-ethyloct-3-yl hexyl ester C18H34O4 27.28 hexadecanoic acid, ethyl ester C18H36O2 28.87 octadecanoic acid, ethyl ester C20H40O2 29.01 eicosyl acetate C22H44O2 Benzenes 6.18 benzene, 1, 3-dimethyl- C8H10 22.84 benzene, 1, 1'-ethylidenebis- C14H14 23.72 benzene, 1, 1'-propylidenebis- C15H16 24.59 benzene, 1, 1'-butylidenebis- C16H18 24.70 benzene, 1, 1'-(3-methyl-1-propene-1, 3-diyl)bis- C17H20 Others 13.72 butanoic acid, anhydride C8H14O3 25.51 tetradecanoic acid C14H28O2 27.05 1-decanol, 2, 2-dimethyl- C12H26O 5.65 furfural C5H4O2 11.82 furan, 2, 5-diethoxytetrahydro- C8H16O3 22.77 octyl-.beta.-d-glucopyranoside C14H28O6 24.25 ethyl.alpha.-d-glucopyranoside C8H16O6 8.11 2H-pyran, 5, 6-dihydro-2-methoxy- C6H10O2 23.09 phenol, 2, 4-bis(1, 1-dimethylethyl)- C14H22O 
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