玉米秸秆催化液化制备生物油实验研究

李润东; 张杨; 李秉硕; 刘合鑫; 开兴平; 烟征; 杨天华

玉米秸秆催化液化制备生物油实验研究

1.
沈阳航空航天大学能源与环境学院辽宁省清洁能源重点实验室, 辽宁沈阳 110136
2.
天津大学环境科学与工程学院, 天津 300072

基金项目:

国家自然科学基金 51576135

辽宁省自然科学基金联合基金 2013024019

详细信息

通讯作者:
杨天华, Tel: 024-89724818, E-mail: thyang@sau.edu.cn

中图分类号: TK6
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- 被引次数: 0
出版历程
- 收稿日期: 2015-08-20
- 修回日期: 2015-11-02
- 网络出版日期: 2022-03-23
- 刊出日期: 2016-01-01

Hydrothermal catalytic liquefaction of corn stalk for preparation of bio-oil

1.
College of Energy and Environment, Shenyang Aerospace University, Key Laboratory of Clean Energy, Shenyang 110136, China
2.
School of Environmental Science and Engineering, Tianjin University, Tianjin 300072, China

Funds:

The project was supported by the National Natural Science Foundation of China 51576135

the Joint Funds of the Natural Science Foundation of Liaoning Province 2013024019

More Information

Corresponding author: YANG Tian-hua, Tel: 024-89724818, E-mail: thyang@sau.edu.cn

摘要

摘要: 以玉米秸秆为原料, 添加分子筛催化剂在体积为500 mL的高温高压反应釜中进行催化液化制备生物油实验研究。选取反应温度、催化剂含量和反应时间三个主要因素为变量, 探究其对玉米秸秆催化液化产物分布的影响。利用气相色谱-质谱联用仪(GC-MS) 和傅里叶红外光谱仪(FT-IR) 对玉米秸秆生物油的成分和官能团结构进行分析。结果表明, 玉米秸秆的最佳催化液化条件为, 反应温度为340 ℃, 玉米秸秆15 g, FeHZSM-5催化剂含量为6.67%, 反应时间为30 min。在此条件下, 生物油产率为28.03%, 催化液化整体转化率为81.73%。生物油的主要成分为酚类和长链酯类, 生物油的热值达30.08 MJ/kg。
- 玉米秸秆 /
- 催化剂 /
- 催化液化 /
- 生物油
Abstract: The hydrothermal catalytic liquefaction of corn stalk (CS) in a 500 mL batch reactor was conducted. The influence of reaction temperature and catalyst quantity as well as reaction time on the products distribution was investigated. The main components and functional groups of bio-oil with and without catalysts were characterized by gas chromatography/mass spectrometry (GC-MS) and Fourier transform infrared spectrometry (FT-IR). The result shows that the optimal conditions of liquefaction are 15 g CS with 6.67% FeHZSM-5 at 340 ℃ for 30 min, at which the bio-oil yield reaches a maximum of 28.03% with the highest CS conversion of 81.73%. The main components of bio-oil are phenols and esters, and the HHV of the bio-oil reaches to 30.08 MJ/kg.
- corn stalk /
- catalyst /
- catalytic liquefaction /
- bio-oil

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图 1 釜内温度和压力随时间的变化

Figure 1 Relationship of the temperature and pressure in the autoclave with the reaction time

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图 2 反应温度对秸秆液化产物分布的影响

Figure 2 Influence of reaction temperature on the yields of products

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图 3 催化剂对秸秆液化产物分布的影响

Figure 3 Influence of catalyst on the yields of products

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图 4 反应时间对秸秆液化产物分布的影响

Figure 4 Influence of residence time on the yields of products

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图 5 添加催化剂前后生物油的FT-IR谱图

Figure 5 FT-IR spectra of the bio-oil obtained with and without catalyst

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图 6 生物油中各类物质的相对含量

Figure 6 Relative content of main groups in bio-oil

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图 7 添加催化剂前后生物油的C-NP图

Figure 7 C-NP gram of bio-oils obtained from liquefaction with and without catalyst

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表 1 玉米秸秆的工业分析与元素分析

Table 1 Proximate, ultimate and heating value analyses of CS material

Proximate analysis w_d/%				Ultimate analysis w_d/%					Heating value Q/(MJ·kg^-1)
M	A	V	FC	C	H	O^a	N	S	Heating value Q/(MJ·kg^-1)
5.45	5.84	74.55	14.16	41.44	5.31	52.27	0.84	0.14	12.25
^a: by difference

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表 2 生物油主要组分的GC-MS分析

Table 2 Major chemical compositions of bio-oil

RT.	M.F.	Compound	Area /%	Time t/min	M.F.	Compound	Area /%
4.602	C₆H₈O	2-cyclopente n-1-one, 2-methyl-	0.42	20.436	C₁₉H₃₈	1-nonadecene	1.10
6.428	C₆H₈O	2-cyclopenten-1-one, 3-methyl-	0.28	20.972	C₁₁H₁₃N	1H-indole, 5, 6, 7-trimethyl-	2.02
9.086	C₆H₆O	phenol	0.77	21.383	C₁₁H₁₃N	2, 3, 7-trimethylindole	1.92
9.870	C₇H₁₀O	2-cyclopenten-1-one,	0.58	21.851	C₁₂H₁₅N	1, 2, 3, 7-tetramethylindole	0.89
		2, 3-dimethyl-
11.391	C₈H₁₂O	2-cyclopenten-1-one,	0.28	22.798	C₁₉H₃₈	1-nonadecene	1.11
		2, 3, 4-trimethyl-
12.375	C₈H₁₂O	2-cyclopenten-1-one, 2-methyl-	0.40	23.247	C₁₃H₂₆	cyclohexane, 2-butyl-	0.96
						1, 1, 3-trimethyl-
12.595	C₇H₈O₂	phenol, 2-methoxy-	0.68	23.362	C₁₅H₃₂O	1-dodecanol, 3, 7, 11-trimethyl-	1.58
12.796	C₈H₁₂O	2-cyclopenten-1-one,	0.74	24.902	C₁₉H₃₈	1-nonadecene	2.06
		3, 5, 5-trimethyl-
13.475	C₇H₈O	phenol, 4-methyl-	0.86	24.997	C₁₇H₃₄O₂	hexadecanoic acid, methyl ester	0.86
13.733	C₈H₁₂O	2-cyclopenten-1-one,	0.80	25.102	C₁₆H₂₂O₄	dibutyl phthalate	1.81
		2, 3, 4-trimethyl-
14.881	C₈H₁₀O	phenol, 3-ethyl-	0.48	25.227	C₁₆H₃₀O₂	9-hexadecenoic acid	2.01
15.072	C₈H₁₀O	phenol, 2, 5-dimethyl-	0.59	25.351	C₁₆H₃₂O₂	n-hexadecanoic acid	2.65
15.321	C₈H₁₀O	phenol, 4-ethyl-	6.63	25.600	C₁₈H₃₆O₂	hexadecanoic acid, ethyl ester	8.71
15.684	C₉H₁₀N₂	1H-benzimidazole, 5, 6-dimethyl-	0.84	25.762	C₁₉H₃₆O₂	10-octadecenoic acid, methyl ester	1.71
15.789	C₁₀H₁₀O	benzofuran, 4, 7-dimethyl-	0.42	26.728	C₁₉H₃₆O₂	16-octadecenoic acid, methyl ester	1.17
15.866	C₁₀H₁₀O	benzofuran, 4, 7-dimethyl-	1.40	26.891	C₁₉H₃₈O₂	heptadecanoic acid,	1.09
						16-methyl-, methyl ester
16.621	C₉H₁₂O	phenol, 2, 4, 6-trimethyl-	1.12	26.996	C₁₈H₃₄O₂	oleic acid	1.09
16.679	C₉H₁₂O	phenol, 3-(1-methylethyl)-	1.12	27.244	C₁₈H₃₆O₂	octadecanoic acid	10.78
16.879	C₉H₈O	1H-inden-1-one, 2, 3-dihydro-	0.71	27.598	C₂₀H₄₀O₂	octadecanoic acid, ethyl ester	4.51
17.032	C₉H₁₂O₂	phenol, 4-ethyl-2-methoxy-	2.84	27.694	C₁₇H₃₆O	1-hexadecanol, 2-methyl-	1.39
17.501	C₁₀H₁₀O	1H-inden-1-one, 2,	0.65	27.780	C₂₆H₅₄	octadecane,	1.15
		3-dihydro-3-methyl-				3-ethyl-5-(2-ethylbutyl)-
17.606	C₁₁H₁₂O	1H-inden-1-one, 2,	1.02	28.487	C₁₉H₃₈O₃	octadecanoic acid,	1.05
		3-dihydro-3, 3-dimethyl-				4-hydroxy-, methyl ester
18.199	C₈H₁₀O₃	phenol, 2, 6-dimethoxy-	1.85	28.545	C₂₂H₄₄	1-docosene	1.05
18.476	C₁₀H₁₄O₂	phenol, 2-methoxy-4-propyl-	1.08	28.621	C₁₆H₃₄O	1-decanol, 2-hexyl-	1.17
19.021	C₁₂H₁₄O	1(2H)-naphthalenone,	1.32	29.377	C₂₆H₅₂	9-hexacosene	0.94
		5-ethyl-3, 4-dihydro-
19.384	C₁₁H₁₆O₂	3-tert-butyl-4-hydroxyanisole	0.80	30.161	C₂₂H₄₄	1-docosene	0.83
19.566	C₉H₁₂O₃	phenol, 4-methoxy-	2.17	32.513	C₃₀H₅₀	squalene	0.86
		3-(methoxymethyl)-
20.149	C₁₀H₁₁N	indolizine, 2, 5-dimethyl-	1.56	33.928	C₂₉H₄₈	stigmasta-4, 22-diene	0.37

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