不同热裂解温度下ZSM-5对玉米秸秆催化热裂解烃类选择性影响

柴美云; 刘荣厚; 赫倚风; 李冲

不同热裂解温度下ZSM-5对玉米秸秆催化热裂解烃类选择性影响

上海交通大学农业与生物学院生物质能工程研究中心, 上海 200240

基金项目:

国家自然科学基金 51776127

详细信息

通讯作者:
刘荣厚Tel: 021 -34205744, E-mail:liurhou@sjtu.edu.cn

中图分类号: S216.2
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- 文章访问数: 155
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- 被引次数: 0
出版历程
- 收稿日期: 2020-02-24
- 修回日期: 2020-04-29
- 网络出版日期: 2021-01-23
- 刊出日期: 2020-05-10

Effect of ZSM-5 on hydrocarbon selectivity of corn stalk catalytic pyrolysis at different pyrolysis temperatures

Biomass Energy Engineering Research Centre, School of Agriculture and Biology, Shanghai Jiao Tong University, Shanghai 200240, China

Funds:

the National Natural Science Foundation of China 51776127

摘要

摘要: 为探讨不同热裂解温度下ZSM-5对玉米秸秆催化热裂解特性及烃类选择性的影响，本研究利用TGA对比有无ZSM-5时玉米秸秆的热裂解失重曲线，利用Py-GC/MS对比玉米秸秆在450、500、550和600 ℃下的热裂解和催化热裂解产物分布。结果表明，ZSM-5的使用可以降低玉米秸秆最高分解速率时对应的热裂解温度，降低温度为23 ℃。未使用ZSM-5时，热裂解产物种类以及烃类选择性均随热裂解温度的升高不断增加，在600 ℃时，烃类选择性达到最高，为11.33%；使用ZSM-5后，烃类产率随热裂解温度的升高先增加后减少，在550℃时，烃类选择性达到最高，为29.24%。使用ZSM-5后，玉米秸秆催化热裂解主要产物中出现了甲苯、茚、萘、二甲基萘等烃类，甲苯的最高产率为4.76%，萘的最高产率为3.96%。
- 玉米秸秆 /
- ZSM-5 /
- 热裂解 /
- TGA /
- Py-GC/MS /
- 烃类选择性
Abstract: In order to study the effect of ZSM-5 on the catalytic pyrolysis characteristic and hydrocarbon selectivity of corn stalk catalytic pyrolysis at different pyrolysis temperatures, the thermogravimetric analysis (TGA) was used to obtain the TG and DTG profiles of corn stalk pyrolysis with and without ZSM-5, and the pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) tests were conducted to analyze the products distribution of corn stalk pyrolysis with and without ZSM-5 at 450, 500, 550, and 600 ℃. The results show that ZSM-5 can decrease the pyrolysis temperature at the highest pyrolysis rate by 23 ℃. Without ZSM-5, both the categories of pyrolysis compounds and the hydrocarbon yield increase with the increase of pyrolysis temperature, and the selectivity of hydrocarbon reaches to the highest value of 11.33% at 600 ℃. However, with ZSM-5, the hydrocarbon yield increases at first and then decreases with the increase of pyrolysis temperature, and the selectivity of hydrocarbon is up to the highest value of 29.24% at 550 ℃. Toluene, indene, naphthalene and 2-methyl-naphthalene are evolved as the main compounds with ZSM-5. And the maximum yields of toluene and naphthalene reach to 4.76% and 3.96%, respectively.
- corn stalk /
- ZSM-5 /
- pyrolysis /
- TGA /
- Py-GC/MS /
- hydrocarbon selectivity

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图 1 玉米秸秆热裂解和催化热裂解的TG曲线(a)和DTG曲线(b)

Figure 1 TG curves (a) and DTG curves (b) of corn stalk pyrolysis with and without catalyst

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图 2 玉米秸秆在不同热裂解温度下的Py-GC/MS总离子流图

Figure 2 Py-GC/MS results of corn stalk at different pyrolysis temperatures

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图 3 玉米秸秆在不同热裂解温度下的热裂解有机产物分布

Figure 3 Organic products selection of corn stalk pyrolysis at different pyrolysis temperatures

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图 4 玉米秸秆在不同温度下的催化热裂解有机产物分布

Figure 4 Organic products selection of corn stalk catalytic pyrolysis at different pyrolysis temperatures

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表 1 玉米秸秆的理化特性

Table 1 Physicochemical characteristics of corn stalk

Item	Value
Proximate analysis (received basis)w/%
M	6.59±0.005
A	5.92±0.07
V	72.83±0.12
FC^a	14.66
Ultimate analysis (dry ash-free basis)w/%
C	46.35±0.04
H	6.96±0.005
O^a	45.84
N	0.06±0.0002
S	0.79±0.003
Composition analysis (received basis)w/%
Cellulose	40.34±0.06
Hemicellulose	25.08±0.38
Lignin	19.23±0.37
Q_{HHV, net}/(MJ·kg^-1)	16.07±0.73
^a: calculated by difference

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表 2 基于Coats-Redfern法处理的玉米秸秆热裂解动力学参数

Table 2 Kinetic parameters with Coats-Redfern method for corn stalk

Sample	Temperaturet/℃	E/(kJ·mol^-1)	A/s^-1	r
Corn stalk	187-415	105.73	5032.73	0.973
Mixture of corn stalk and ZSM-5	171-467	91.28	243.69	0.964

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表 3 玉米秸秆在不同温度下的15种主要催化热裂解产物及其相对含量

Table 3 Main compounds and their relative content of corn stalk catalytic pyrolysis at different pyrolysis temperatures

No.	Name	Molecular formula	Relative content /%
No.	Name	Molecular formula	450℃	500℃	550℃	600℃
1	carbon dioxide	CO₂	18.87	14.15	14.87	12.78
2	methyl glyoxal	C₃H₄O₂	7.30	7.34	8.30	7.44
3	2-propanone, 1-hydroxy-	C₃H₆O₂	3.11	3.07	2.68	3.36
4	toluene	C₇H₈	4.76	1.69	3.33	2.79
5	furfural	C₅H₄O₂	3.92	3.15	3.17	3.31
6	benzene, 1, 3-dimethyl-	C₈H₁₀	0.45	3.41	4.36	3.15
7	benzene, 1-ethyl-2-methyl-	C₉H₁₂	2.16	0.27	0.46	0.34
8	valeramide, 5-chloro-N-methyl-	C₆H₁₂ClNO	4.48	3.13	3.07	2.09
9	indene	C₉H₈	-	-	0.56	0.44
10	naphthalene	C₁₀H₈	1.11	2.32	3.96	2.77
11	benzofuran, 2, 3-dihydro-	C₈H₈O	6.78	6.47	5.48	6.63
12	naphthalene, 2-methyl-	C₁₁H₁₀	2.07	2.90	3.48	2.04
13	2-methoxy-4-vinylphenol	C₉H₁₀O₂	4.21	4.45	3.99	3.80
14	naphthalene, 1, 6-dimethyl-	C₁₂H₁₂	1.18	1.27	1.26	0.54
15	stigmasta-3, 5-diene	C₂₉H₄₈	0.36	0.41	0.38	0.36

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