生物质与塑料共热解协同作用研究

doi:10.3969/j.issn.0253-2417.2019.03.005

摘要/Abstract

摘要：

利用固定床反应器研究了木屑与低密度聚乙烯（LDPE）共热解时的热解行为，并以木屑、LDPE单独热解为对照，考察了热解温度对共热解行为的影响，结果表明：木屑与LDPE共热解可以提高液体产率，当热解温度为600℃时液体产率达到最大值56.84%，比理论值高6.44个百分点。通过GC-MS对生物质与LDPE共热解液体产物组成进行了分析，发现共热解产生的生物油组分主要为脂肪烃、醇类及酚类，共热解过程中还生成了某些特定组分，如十一醇、庚烯醛等含氧长链化合物，这是生物质与LDPE共热解时自由基相互作用的产物。通过热重-红外联用实验研究了木屑与LDPE共热解的协同作用，结果发现：共热解时最大反应速率温度为490℃，相比LDPE单独热解时的512℃降低22℃；木质素裂解过程中产生的羟基自由基会与LDPE裂解产生的小分子产物结合形成十一醇、辛基苯酚等物质，而纤维素热解过程中生成的呋喃类、醛类会与LDPE裂解产生的C_nH_m分子结合形成2-丁基四氢呋喃、庚烯醛、十二醛等物质。

关键词: 生物质, 共热解, 低密度聚乙烯, 生物油

Abstract:

The co-pyrolysis activities of sawdust/low-density polyethylene(LDPE) were studied in fixed-bed reactor. The effect of temperature on the co-pyrolysis behavior was also investigated by comparing with sawdust and LDPE individually. The results showed that the bio-oil yield could be effectively improved by the co-pyrolysis process, the maximum bio-oil yield(56.84%) was obtained at 600℃, which was 6.44 percentage point higher than the theoretical value. The composition of biomass and LDPE co-pyrolysis liquid products was analyzed by GC-MS. It was found that the bio-oil components produced by co-pyrolysis were mainly aliphatic hydrocarbons, alcohols and phenols. Some specific components, such as undecanol, heptenal and other oxygen-containing long-chain compounds, were also produced during the co-pyrolysis process, which was the product of free radical interaction between biomass and LDPE. The synergistic effect of co-pyrolysis of sawdust and LDPE was studied by thermogravimetry-infrared spectroscopy. The results showed that the maximum reaction rate temperature during co-pyrolysis was 490℃, which was about 22℃ lower than 512℃, which was the temperature of maximum reaction rate in LDPE individual pyrolysis. The hydroxyl radical generated during the lignin cracking process combining with the small molecular produced by the cleavage of LDPE formed undecanol, octyl-phenol and the like, and the furans and aldehydes formed during the pyrolysis of cellulose were reacted with the resulting C_nH_m formed by cleavage of LDPE to obtain the substances such as 2-butyltetrahydrofuran, heptenal, dodecanal or the like.

Key words: biomass, co-pyrolysis, low density polyethylene, bio-oil

中图分类号:

TQ35

刘世奇,张素平,于泰莅,蔡勤杰. 生物质与塑料共热解协同作用研究[J]. 林产化学与工业, 2019, 39(3): 34-42.

Shiqi LIU,Suping ZHANG,Taili YU,Qinjie CAI. Synergistic Effect of Co-pyrolysis of Biomass and Plastics[J]. Chemistry and Industry of Forest Products, 2019, 39(3): 34-42.

图/表 8

表1

图1

图2

表2

不同温度下木屑与LDPE共热解的生物油组成"

编号 No.	组分 component	GC含量GC content/%
编号 No.	组分 component	500 ℃	600 ℃	700 ℃
1	十一烷undecane	—	2.48	7.19
2	正十二烷dodecane	—	—	8.33
3	环十二烷cyclododecane	—	—	5.61
4	正十四烷tetradecane	—	—	6.17
5	正十六烷hexadecane	5.5	7.76	—
6	环十六烷cyclohexadecane	5.47	2.31	—
7	正十九烷nonadecane	12.24	11.39	1.89
8	1-十一烯1-undecene	—	—	5.05
9	1-十二烯1-dodecene	—	—	9.51
10	十四烯tetradecene	—	—	3.13
11	十八烯octadecene	3.64	—	—
12	1-二十二烯1-docosene	4.23	—	—
13	乙酸acetic acid	8.93	7.70	5.23
14	乙酸甲酯acetic acid, methyl ester	3.31	4.24	1.59
15	糠醇2-furanmethanol	1.50	1.64	—
16	愈创木酚2-methoxy-phenol	4.11	4.43	2.70
17	2-甲氧基-4-甲基苯酚2-methoxy-4-methyl-phenol	2.77	2.93	2.86
18	4-乙基愈创木酚4-ethyl-2-methoxy-phenol	2.18	1.66	2.02
19	4-甲基愈创木酚2-methoxy-4-methyl-phenol	3.81	5.62	3.86
20	邻苯二酚1, 2-benzenediol	1.68	1.91	—
21	2-辛基苯酚2-octyl-phenol	—	0.93	1.51
22	苯酚phenol	3.51	4.60	2.43
23	2, 6-二甲氧基苯酚2, 6-dimethoxy-phenol	1.37	1.07	0.95
24	对甲酚4-methyl-phenol	0.95	1.52	1.97
25	γ-丁内酯γ-butyrolactone	0.97	0.91	—
26	2-甲氧基-4-(1-丙烯基)苯酚2-methoxy-4-(1-propenyl)-phenol	—	1.28	1.02
27	乙酰氧基丙酮1-acetyloxy-2-propanone	1.87	1.50	0.95
28	甲基环戊烯醇酮methyl cyclopentenolone	2.03	1.62	—
29	3-呋喃甲醇3-furanmethanol	1.40	3.05	—
30	丙酸propanoic acid	0.90	—	—
31	十一醇undecanol	1.52	2.09	1.21
32	十三烷醇n-tridecanol	2.14	2.91	1.86
33	2-庚烯醛2-heptenal	2.95	—	—
34	1-十七烷醇1- n-heptadecanol	4.25	9.00	2.19
35	十二醛dodecanal	2.81	—	—
36	十三烷醇n-tridecanol	—	—	2.51
37	1-十六烷醇1-hentetracontanol	—	—	2.78
38	十八醛octadecenal	8.89	13.15	3.06
39	3, 7-二甲基-1-辛醇3, 7dimethyl-1-octanol	1.04	—	2.04
40	2-甲基丁二酸环己基酯2-methyl butanoic acid cyclohexyl ester	1.34	1.38	1.73
41	1, 4-丁二醇二乙酸酯1, 4-diacetate butandiol	1.19	0.92	0.85
42	6-甲基-2-庚基乙酸酯6-methyl-2-heptanol acetate	—	—	1.81
43	十八烷基环戊二烯酸octadecyl cyclopentadienoic acid	—	—	0.92
44	环扁桃酯cyclandelate	—	—	2.56
45	2-丁基四氢呋喃2-butyltetrahydro-furan	—	—	1.06
46	2-羟基-5-甲基苯乙酮2-hydroxy-5-methylphenyl-ethanone	—	—	1.46
47	四氢糠醇2-tetrahydro-furanmethanol	2.11	—	—

表2

图3

图4

表3

表4

半纤维素、纤维素500 ℃热解时的生物油组分"

半纤维素热解油bio-oil of hemicellulose
组分 component	GC含量/% GC content
2, 2-二乙基-3-甲基-恶唑烷 2, 2- diethyl-3-methyl-oxazolidine	13.39
3, 4-二氢-6-羟基-2H-1-苯并吡喃-2-酮 3, 4-dihydro-6-hydroxy-2H-1-benzopyran-2-one	12.51
1-羟基-2-丁酮1-hydroxybutan-2-one	10.77
1-戊烯-3-醇1-penten-3-ol	9.27
糠醛furfural	9.14
1, 3-二氧杂环戊烯-2-酮 1, 3-dioxol-2-one	6.71
4-甲基-5-(2-氧代亚丙基)呋喃-2-酮 4-methyl-5-(2-oxo-propylidene)furan-2-one	5.15
甲酸formic acid	4.62
3-甲基-2-羟基-2-环戊烯酮 3-hydroxy-2-methyl-1-2-cyclopenten-1-one	3.62
5-甲基-2(3H)-呋喃酮5-methyl-2(3H)-furanone	3.47
1-乙基-4-甲基环己烷1-ethyl-4-methylcyclohexane	3.12
1, 2-环氧-2-甲基丁烷1, 2-epoxy-2-methylbutane	2.96
乙酸acetic acid	2.88
2, 3-二羟基苯甲醛2, 3-dihydroxybenzaldehyde	2.29
邻苯二酚catechol	1.84
6-甲基二氢-2H-吡喃-3(4H)-酮 6-methyl dihydro-2H-pyran-3(4H)-one	1.78
糠醇2-furanylmethanol	1.71
2-氧代丁酸甲酯2-oxo-butanoic acid methyl ester	1.68
乙二醛glyoxal	1.47
D-阿洛糖D-allose	81.7
1, 6-脱水-β-D-呋喃葡萄糖 1, 6-anhydro-beta-D-glucofuranose	5.68
2-乙烯基-4-甲基-1, 3-二氧戊环 2-ethenyl-4-methyl-1, 3-dioxolane	3.15
左旋葡萄糖酮levoglucosenone	1.41
5-壬酮5-nonanone	1.16
3-乙基-哌啶-2, 6-二酮3-ethyl-piperidine-2, 6-dione	0.93
糠醛furfural	0.86
氰基甲酸乙酯carbonocyanidic acid, ethyl ester	0.72
恶唑烷2, 2-二乙基-3-甲基2, 2-diethyl-3-methyl oxazolidine	0.57
5-甲基呋喃醛5-methyl-2-furaldehyde	0.38
1, 6-脱水-β-D-葡萄糖1, 6-anhydro-β-D-glucopyranose	0.37
2, 5-呋喃二甲醛2, 5-furandicarbaldehyde	0.34
乙烯基甲醚methoxy-ethene	0.33
异丁烯2-methyl-1-propene	0.25
2(5H)-呋喃酮2(5H)-furanone	0.15
5-甲基-2(3H)-呋喃酮5-methyl-2(3H)-furanone	0.15
1, 2, 5, 6-四氢吡啶1, 2, 5, 6-tetrahydropyridine	0.15
1-(2-亚甲基环丙基)乙酮 1-(2-methylidenecyclopropyl)ethanone	0.14
甲基环戊烯醇酮methyl cyclopentenolone	0.07

表4

参考文献 12

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样品 samples	工业分析 proximate analysis/%				元素分析 ultimate analysis/%
样品 samples	水分 moisture	灰分 ash	挥发分 volatile matter	固定碳 fixed carbon	C	H	O	N
木屑sawdust	10.98	13.83	63.59	11.50	45.41	4.9	49.39	0.3
LDPE	0	0.3	99.7	0	85.5	14.5	0	0

组分 component	GC含量/% GC content
愈创木酚2-methoxyphenol	34.7
4-羟基-3-甲氧基苯甲醛vanillin	11.7
4-羟基-3-甲氧基苯乙酮apocynin	6.99
4-乙烯基-2-甲氧基苯酚2-methoxy-4-vinylphenol	6.82
4-甲基愈创木酚creosol	4.65
(E)-2-甲氧基-4-(1-丙烯基苯酚)trans-isoeugenol	3.98
4-羟基-3-甲氧基苯丙酮1-(4-hydroxy-3-methoxyphenyl)- 2-propanone	3.74
4-乙基愈创木酚4-ethyl-2-methoxyphenol	3.31
苯酚phenol	3.14
邻苯二甲醚1, 2-dimethoxybenzene	3.08
2-甲氧基-6-甲基苯酚2-methoxy-6-methylphenol	3.01
4-羟基-3-甲氧基苯乙酸homovanillic acid	2.44
2-甲基苯酚2-methyl-phenol	2.31
2-甲氧基-4-丙基-苯酚2-methoxy-4-propylphenol	2.1
4((1E)-羟基-1-丙烯基)-2-甲氧基苯酚 4-((1E)-hydroxy-1-propenyl)-2-methoxy phenol	1.97
2，4-二甲氧基苯乙酮2, 4-dimethoxyacetophenone	1.84
4-甲基苯酚p-cresol	1.74
3, 4-二甲氧基苯甲醛3, 4-dimethoxy-benzaldehyde	1.6
4-乙氧基-3-甲氧基苯甲醛4-ethoxy-3-anisaldehyde	0.73

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