<i>N</i>-叔丁基-<i>α</i>-苯基硝酮对纤维素超临界乙醇液化产物分布的影响

黎巍; 汤楚翘; 解新安; 李雁; 李璐; 孙娇; 樊荻; 魏星

N-叔丁基-α-苯基硝酮对纤维素超临界乙醇液化产物分布的影响

华南农业大学食品学院, 广东广州 510640

基金项目:

国家自然科学基金 21576107

国家自然科学基金 21176097

广东省科技计划项目 2014A010106024

详细信息

通讯作者:
解新安, Tel:020-8528 0266, E-mail:xinanxie@scau.edu.cn

中图分类号: TK6
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- PDF下载量: 4
- 被引次数: 0
出版历程
- 收稿日期: 2016-08-18
- 修回日期: 2016-10-09
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-01-10

Effects of N-tert-butyl-α-phenylnitrone on the product distribution of cellulose liquefaction in supercritical ethanol

College of Food Science, South China Agricultural University, Guangzhou 510640, China

Funds:

National Natural Science Foundation of China 21576107

National Natural Science Foundation of China 21176097

and Guangdong Provincial Science and Technology Program Foundation of China 2014A010106024

摘要

摘要: 以N-叔丁基-α-苯基硝酮（PBN）为自由基结合剂，采用间歇式高温高压反应釜对玉米秸秆纤维素进行超临界乙醇液化，考察PBN用量（浓度）和反应温度（活性）对纤维素液化产物及生物油中主要化合物分布的影响。结果表明，在320℃，仅有超临界乙醇作用，生物油收率为37.17%，挥发分收率高达50.08%；随着PBN用量增加到0.4 g，生物油收率最高提升至48.35%，挥发分最低下降到35.65%。在超临界乙醇和PBN作用下，随着反应温度从250℃升高至340℃，纤维素转化率从23.10%急剧增加至88.92%，生物油收率从19.18%上升到最高48.35%（320℃）后略有下降，挥发分也从6.03%急剧上升至50.28%。GC-MS结果显示，酯类、酮类、烃类、醇类、酸类及苯类化合物是生物油的主要成分，各组分的最高相对含量分别为27.91%、15.77%、13.44%、12.42%、16.07%、19.81%。实验结果证实了PBN对纤维素超临界乙醇液化产物及生物油组分分布产生了较明显的影响，尤其能通过与含苯基、乙基等活性碎片结合促进挥发分与生物油之间的转化，且PBN用量及液化温度的改变可以促使生物油中主要化合物发生不同程度的相互转化。
- 纤维素 /
- 液化 /
- 超临界乙醇 /
- N-叔丁基-α-苯基硝酮
Abstract: With N-tert-butyl-α-phenylnitrone (PBN) as free radicals trapper, the effects of PBN dosage and reaction temperature on the product distribution and bio-oil component distribution of cellulose liquefaction in supercritical ethanol were investigated using an autoclave. The results showed that the yields of bio-oil and volatile compounds were 37.17% and 50.08% without PBN, respectively; meanwhile the highest yield of bio-oil increased to 48.35%, whereas the volatile compound yield decreased to 35.65% with the PBN dosage increased from 0 to 0.4 g. With the increase of reaction temperature from 250℃ to 340℃, the cellulose conversion rate increased sharply from 23.10% to 88.92% while the bio-oil yield increased from 19.18% to 48.35% (320℃) and the volatile compound yield increased from 6.03% to 50.28% quickly. The GC-MS results showed that the dominant compounds in bio-oil were esters, ketones, alkanes, alcohols, acids and benzenes with the highest relative contents of 27.91%, 15.77%, 13.44%, 12.42%, 16.07% and 19.81%, respectively. The present results proved that PBN has obvious effects on the product distribution and bio-oil component distribution of cellulose liquefaction in supercritical ethanol, especially PBN can enhance the transformation between bio-oil and volatile compounds via reacting with benzyl radicals, methyl radicals, ethyl radicals, etc. The transformation among dominant compounds in bio-oil can be regulated by varying PBN dosage and reaction temperature.
- cellulose /
- liquefaction /
- supercritical ethanol /
- N-tert-butyl-α-phenylnitrone

HTML全文

图 1 PBN的化学结构示意图

Figure 1 Chemical structure of PBN

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图 2 纤维素超临界乙醇/PBN液化实验流程示意图

Figure 2 Procedures for the liquefaction of cellulose in supercritical ethanol with PBN (gas products, GAS; bio-oil, BO; residue, RE)

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图 3 不同PBN用量下纤维素转化率及液化产物收率

Figure 3 Effect of the PBN dosage on the yields of various products & conversion rate for cellulose liquefaction in 100 mL ethanol under 8.6-9.6 MPa and 320 ℃ for 60 min

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图 4 不同PBN用量下纤维素液化残渣的FT-IR谱图

Figure 4 FT-IR analysis for RE obtained from cellulose liquefaction with various dosage of PBN in 100 mL ethanol under 8.6-9.6 MPa and 320 ℃ for 60 min

a: 0 g; b: 0.1 g; c: 0.2 g; d: 0.3 g; e: 0.4 g absorption peak^[25-27]: 1 060-1 160 cm^-1 C-O-C; 1 680-1 715 cm^-1 -C=O; 1 710-1 770 cm^-1 -COOH; 2 900-3 100 cm^-1 -C-H; 3 300-3 600 cm^-1 -O-H

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图 5 不同反应温度下纤维素转化率及液化产物收率

Figure 5 Effect of reaction temperature on the yields of various products & conversion rate of cellulose liquefaction in 100 mL ethanol and 0.2 g PBN under 6.4-10.2 MPa for 60 min

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图 6 不同反应温度下纤维素液化残渣的FT-IR谱图

Figure 6 FT-IR analysis for RE obtained from cellulose liquefaction with various reaction temperatures in 100 mL ethanol and 0.2 g PBN under 6.4-10.2 MPa for 60 min

a: 250 ℃; b: 280 ℃; c: 300 ℃; d: 320 ℃; e: 340 ℃ absorption peak: 1 060-1 160 cm^-1 C-O-C; 1 680-1 715 cm^-1 -C=O; 1 710-1 770 cm^-1 -COOH; 2 900-3 100 cm^-1 -C-H; 3 300-3 600 cm^-1 -O-H

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图 7 不同PBN用量生物油中主要化合物的相对含量

Figure 7 Relative contents of dominant compounds in BO with various dosage of PBN for cellulose liquefaction in 100 mL ethanol under 8.6-9.6 MPa and 320 ℃ for 60 min

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表 1 不同PBN用量下纤维素超临界乙醇液化生物油产物GC-MS分析

Table 1 GC-MS analysis for BO with various dosage of PBN for cellulose liquefaction in 100 mL ethanol under 8.6-9.6 MPa and 320 ℃ for 60 min

RT t/min	Name of compounds	Formula	Area/%
RT t/min	Name of compounds	Formula	0.1 g	0.2 g	0.3 g	0.4 g
Esters
5.335	propanoic acid, 2-hydroxy-2-methyl-, ethyl ester	C₆H₁₂O₃	0.27	-	0.21	0.17
5.867	2-butenoic acid, ethyl ester, (E)-	C₆H₁₀O₂	2.09	1.99	2.19	2.76
6.054	pentanoic acid, propyl ester	C₈H₁₆O₂	0.29	0.27	-	-
6.065	butanoic acid, 2-methyl-, ethyl ester	C₇H₁₄O₂	-	-	0.15	0.32
7.552	tetrahydrofurfuryl acrylate	C₈H₁₂O₃	0.48	0.50	-	-
7.737	2-propenoic acid, butyl ester	C₇H₁₂O₂	0.70	0.66	0.74	0.58
7.845	ethyl 2-methyl cyclopropanecarboxylate	C₇H₁₂O₂	0.19	0.18	0.21	-
7.904	octanoic acid, ethyl ester	C₁₀H₂₀O₂	0.89	0.80	-	-
7.911	pentanoic acid, ethyl ester	C₇H₁₄O₂	-	-	0.83	1.07
8.045	butanoic acid, 2-hydroxy-, ethyl ester	C₆H₁₂O₃	4.06	4.05	-	-
8.405	acetic acid, ethoxy-, ethyl ester	C₆H₁₂O₃	0.83	0.66	0.44	0.87
8.653	4-pentenoic acid, ethyl ester	C₇H₁₂O₂	0.58	0.62	0.62	0.61
8.717	propanoic acid, 2-(1-ethoxyethoxy)-, ethyl ester	C₉H₁₈O₄	-	2.42	-	-
9.252	ethyl tiglate	C₇H₁₂O₂	0.19	0.21	0.18	0.12
9.567	ethyl trans-2-pentenoate	C₇H₁₂O₂	0.39	0.37	0.35	0.38
10.096	butanoic acid, 2-hydroxy-3-methyl-, ethyl ester	C₇H₁₄O₃	0.41	0.39	0.50	0.32
13.196	pentanoic acid, 4-oxo-, ethyl ester	C₇H₁₂O₃	0.60	0.71	0.41	0.29
13.292	ethyl 2, 4-dioxovalerate	C₇H₁₀O₄	0.52	0.50	-	-
14.009	pentanoic acid, 2-methyl-4-oxo-, ethyl ester	C₈H₁₄O₃	0.23	0.18	-	-
14.136	ethyl dl-2-hydroxycaproate	C₈H₁₆O₃	0.43	0.39	0.32	0.35
14.281	isophytol, acetate	C₂₂H₄₂O₂	-	0.64	0.41	-
15.408	2-(2-methylpropenyl) cyclopropanecarboxylic	C₁₈H₃₀O₂	1.18	1.21	1.06	0.84
	acid, 2-isopropyl-5-methyl-cyclohexyl ester
16.120	benzoic acid, ethyl ester	C₉H₁₀O₂	0.29	0.34	0.50	0.46
16.454	butanedioic acid, diethyl ester	C₈H₁₄O₄	0.77	0.69	0.50	-
16.541	5-keto-2, 2-dimethylheptanoic acid, ethyl (ester)	C₁₁H₂₀O₃	0.33	-	0.53	0.35
17.119	diethyl methyl succinate	C₉H₁₆O₄	1.06	1.01	0.83	0.73
17.650	2-propenoic acid, 6-methylheptyl ester	C₁₁H₂₀O₂	0.23	0.32	0.35	0.41
17.905	diethyl malonic acid, 4-methoxyphenyl pentyl ester	C₁₉H₂₈O₅	-	-	0.18	0.38
18.057	benzeneacetic acid, ethyl ester	C₁₀H₁₂O₂	-	0.37	0.35	-
18.670	hexanoic acid, 3-oxo-, ethyl ester	C₈H₁₄O₃	0.54	0.48	0.27	-
19.022	pentanedioic acid, diethyl ester	C₉H₁₆O₄	0.91	0.96	0.41	0.52
19.168	hexanedioic acid, monoethyl ester	C₈H₁₄O₄	1.14	1.12	0.32	0.67
19.842	pentanoic acid, 3, 4, 4-trimethyl-, ethyl ester	C₁₀H₂₀O₂	0.58	0.62	-	-
20.630	benzenepropanoic acid, ethyl ester	C₁₁H₁₄O₂	-	0.16	0.18	0.15
20.967	diethyl pimelate	C₁₁H₂₀O₄	0.54	0.62	0.30	-
21.854	oxalic acid, bis (6-ethyloct-3-yl) ester	C₂₂H₄₂O₄	0.14	0.69	-	0.17
22.010	2, 4-pentadienoic acid, 3, 4-dimethyl-, isopropyl ester	C₁₀H₁₆O₂	-	-	0.18	0.23
22.178	4-(4-methoxycarbonylbutyl)-4-butanolide	C₁₀H₁₆O₄	-	-	0.27	0.38
22.527	cyclopropanecarboxylic acid, 2, 2-dimethyl-	C₁₁H₁₈O₂	0.23	-	0.18	-
	3-(2-propenyl)-, ethyl ester, trans-
26.994	benzenepropanoic acid, 3, 5-bis (1, 1-dimethylethyl)-	C₁₈H₂₈O₃	0.21	-	-	0.17
	4-hydroxy-, methyl ester
27.061	l-(+)-ascorbic acid 2, 6-dihexadecanoate	C₃₈H₆₈O₈	0.58	0.62	0.32	0.52
27.289	hexadecanoic acid, ethyl ester	C₁₈H₃₆O₂	1.08	1.21	1.54	1.19
28.024	9-octadecenoic acid (Z)-, octadecyl ester	C₃₆H₇₀O₂	-	-	0.41	-
29.031	octacosyl acetate	C₃₀H₆₀O₂	1.14	0.18	0.30	-
34.003	bis (2-ethylhexyl) phthalate	C₂₄H₃₈O₄	0.56	0.53	0.80	0.81
Ketones
5.571	2-cyclopenten-1-one	C₅H₆O	0.50	0.55	0.32	0.44
5.640	cyclopentanone, 2-methyl-	C₆H₁₀O	0.72	0.73	0.80	0.93
5.761	2-pentanone, 4-hydroxy-4-methyl-	C₆H₁₂O₂	3.81	3.82	5.41	6.76
7.560	cyclohexanone	C₈H₁₄O	-	-	0.47	0.52
8.335	ethanone, 1-(2-furanyl)-	C₆H₆O₂	0.23	0.25	0.24	-
9.106	cyclopentanone, 2-ethyl-	C₇H₁₂O	0.19	0.21	0.21	0.55
9.170	2-cyclopenten-1-one, 2, 3-dimethyl-	C₇H₁₀O	0.60	1.35	0.95	0.75
11.083	cyclohexanone, 3-ethyl-	C₈H₁₄O	0.17	-	0.24	0.15
12.155	2-cyclopenten-1-one, 2-hydroxy-3-methyl-	C₆H₈O₂	-	0.66	0.27	-
12.935	2-cyclopenten-1-one, 3-ethyl-2-hydroxy-	C₇H₁₀O₂	1.24	1.92	1.51	0.93
13.125	2-cyclopenten-1-one, 3, 4, 4-trimethyl-	C₈H₁₂O	0.35	-	-	0.26
13.496	2-acetylcyclopentanone	C₇H₁₀O₂	0.23	-	0.21	-
15.506	1, 3-cyclopentanedione, 2-ethyl-2-methyl-	C₈H₁₂O₂	1.72	1.83	1.80	-
17.770	2-cyclohexen-1-one, 2-hydroxy-3-	C₁₀H₁₆O₂	1.72	1.92	1.71	1.13
	methyl-6-(1-methylethyl)-
18.590	1(2H)-naphthalenone, 2-(1, 1-dimethylethyl)-	C₁₄H₁₈O	0.83	-	-	-
	3, 4-dihydro-
24.455	benzophenone	C₁₃H₁₀O	-	0.32	-	-
26.864	7, 9-di-tert-butyl-1-oxaspiro (4, 5) deca-6	C₁₇H₂₄O₃	0.29	0.23	0.18	0.29
	9-diene-2, 8-dione
Alkanes
7.450	4-octene, (E)-	C₈H₁₆	0.23	0.18	0.24	0.17
8.714	ethane, 1, 1-diethoxy-	C₆H₁₄O₂	3.00	-	2.10	2.26
9.701	2-methyl-2-octene	C₉H₁₈	0.25	-	-	0.15
10.887	cyclohexene, 4, 4-dimethyl-	C₈H₁₄	-	0.27	0.15	-
12.872	dodecane, 4, 6-dimethyl-	C₁₄H₃₀	0.60	0.62	1.00	1.07
15.123	cyclohexane, (1-methylethylidene)-	C₉H₁₆	-	0.27	0.27	-
16.620	1-dodecene	C₁₂H₂₄	0.37	-	-	0.32
18.475	nonadecane, 9-methyl-	C₂₀H₄₂	0.14	-	0.42	0.26
18.907	heptadecane, 8-methyl-	C₁₈H₃₈	0.81	0.75	0.15	0.20
19.295	nonane, 3-methyl-5-propyl-	C₁₃H₂₈	0.14	-	0.27	-
21.495	tetradecane	C₁₄H₃₀	0.25	0.32	0.24	0.20
21.852	eicosane	C₂₀H₄₂	3.31	2.97	1.60	2.15
22.280	heptadecane	C₁₈H₃₈	0.39	0.41	0.32	-
22.409	heneicosane	C₂₁H₄₄	0.89	1.23	1.21	1.39
23.629	2-methylhexacosane	C₂₇H₅₆	0.49	0.18	-	0.35
24.017	hexadecane	C₁₆H₃₄	0.33	0.18	0.18	-
24.235	tetradecane, 4-methyl-	C₁₅H₃₂	-	0.23	0.30	0.15
24.503	pentadecane, 2, 6, 10, 14-tetramethyl-	C₁₉H₄₀	-	0.39	0.30	0.81
24.599	decane, 1, 1′-oxybis-	C₂₀H₄₂O	-	0.30	0.27	0.35
24.755	undecane, 5-ethyl-5-propyl-	C₁₆H₃₄	-	0.30	-	0.32
24.861	tetracontane	C₄₄H₉₀	0.21	-	0.38	-
24.863	hexadecane, 2, 6, 10, 14-tetramethyl-	C₂₀H₄₂	0.17	-	-	0.81
25.300	5, 5-diethylpentadecane	C₁₉H₄₀	-	0.25	0.21	-
25.515	heptadecane, 2-methyl-	C₁₈H₃₈	0.14	0.30	-	0.35
26.808	5, 5-diethylheptadecane	C₂₁H₄₄	0.46	0.59	0.50	0.35
Alcohols
7.675	3-hexanol, 2-methyl-	C₇H₁₆O	0.14	4.30	4.19	3.89
8.055	o-menthan-8-ol	C₁₀H₂₀O	-	-	3.63	3.68
8.170	ethanol, 2-butoxy-	C₆H₁₄O₂	0.72	0.85	1.03	0.96
11.181	1, 2-pentanediol	C₅H₁₂O₂	4.41	-	-	-
12.345	benzyl alcohol	C₇H₈O	0.21	1.03	0.89	1.10
12.397	4-nonanol	C₉H₂₀O	0.27	-	0.50	0.73
13.297	4-methyl-1, 6-heptadien-4-ol	C₈H₁₄O	-	-	0.47	0.32
14.283	cyclohexanol, 2-(1-methylethyl)-	C₉H₁₈O	0.62	-	-	-
16.364	2H-pyran-2-methanol, tetrahydro-	C₆H₁₂O₂	-	1.07	-	0.81
19.849	4-heptanol, 2, 6-dimethyl-4-(1-methylethyl)-	C₁₂H₂₆O	-	-	0.44	-
21.858	1-dodecanol, 2-octyl-	C₂₀H₄₂O	0.17	0.21	0.53	0.29
Acids
8.365	butanoic acid, 4-hydroxy-	C₄H₈O₃	0.21	0.27	-	-
9.702	2-propenoic acid, 2-methyl-, 2-methylpropyl ester	C₈H₁₄O₂	-	0.16	0.27	-
12.043	2-hexenoic acid, 3, 4, 4-trimethyl-5-oxo-, (Z)-	C₉H₁₄O₃	0.21	-	0.21	-
13.569	butanoic acid, anhydride	C₈H₁₄O₃	15.28	15.45	16.07	15.64
13.732	2-oxopentanedioic acid	C₅H₆O₅	1.93	-	0.62	0.61
28.612	octadecanoic acid	C₁₈H₃₆O₂	0.14	0.18	0.18	-
Others
5.066	2-ethoxytetrahydrofuran	C₆H₁₂O₂	2.98	2.74	2.42	3.25
8.240	2H-pyran, 2-ethoxytetrahydro-	C₇H₁₄O₂	0.58	0.50	0.59	0.81
8.390	furan, tetrahydro-2-methyl-	C₅H₁₀O	-	-	0.18	0.26
18.250	2, 2-diethoxytetrahydrofuran	C₈H₁₆O₃	0.21	0.23	0.18	-
9.869	benzaldehyde	C₇H₆O	0.39	1.01	1.24	1.16
16.364	pentanal, 5-[(tetrahydro-2H-pyran-2-yl) oxy]-	C₁₀H₁₈O₃	1.28	-	1.18	-
18.784	acrolein, 3-ethoxy-, diethyl acetal	C₉H₁₈O₃	0.43	0.48	-	-
21.658	tridecanal	C₁₃H₂₆O	0.37	0.37	0.32	0.67
13.110	mequinol	C₇H₈O₂	-	0.37	-	-
15.635	phenol, 2-ethoxy-	C₈H₁₀O₂	0.31	0.30	0.30	-
23.102	phenol, 2, 4-bis (1, 1-dimethylethyl)-	C₁₄H₂₂O	1.28	1.26	1.03	1.45
8.495	benzene, (1-methylethyl)-	C₉H₁₂	11.02	10.81	14.92	17.93
10.476	.alpha.-methylstyrene	C₉H₁₀	0.48	0.46	0.68	0.75
15.817	benzene, [1-[[1-(1-methylethyl)-3-butenyl]oxy]ethyl]-	C₁₅H₂₂O	1.04	1.30	-	1.13
-: not detected or less than 0.1%

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