镍基催化剂催化木醋液重整制氢实验研究

梁昌明; 张安东; 李志合; 李玉峰; 王绍庆; 易维明

doi:10.19906/j.cnki.JFCT.2021016

镍基催化剂催化木醋液重整制氢实验研究

doi: 10.19906/j.cnki.JFCT.2021016

梁昌明^{1, 2,},
张安东^{1, 2},
李志合^{1, 2, ,},
李玉峰^{1, 2},
王绍庆^{1, 2},
易维明^{1, 2}

1.
山东理工大学农业工程与食品科学学院，山东淄博 255000
2.
山东省清洁能源工程技术研究中心，山东淄博 255000

基金项目: 国家重点研发计划项目（2019YFD1100600），国家自然科学基金（51606113）和山东省自然科学基金（ZR2020ME185）资助

详细信息

通讯作者:
Tel: 18678191880, E-mail: lizhihe@sdut.edu.cn

中图分类号: O643
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- 被引次数: 0
出版历程
- 收稿日期: 2020-10-15
- 修回日期: 2020-11-20
- 刊出日期: 2021-02-08

Hydrogen production from wood vinegar reforming over cobalt modified nickel-based catalyst

LIANG Chang-ming^{1, 2
,},
ZAHNG An-dong^{1, 2},
LI Zhi-he^{1, 2
, ,},
LI Yu-feng^{1, 2},
WANG Shao-qing^{1, 2},
YI Wei-ming^{1, 2}

1.
College of Agricultural Engineering and Food Science, Shandong University of Technology, Zibo 255000, China
2.
Shandong Research Center of Engineering & Technology for Clean Energy, Zibo 255000, China

Funds: The project was supported by National Key Research and Development Program of China (2019YFD1100600), National Natural Science Foundation of China (51606113) and Natural Science Foundation of Shandong Province (ZR2020ME185)

More Information

Corresponding author: Tel: 18678191880, E-mail: lizhihe@sdut.edu.cn

摘要

摘要: 为了实现木醋液的高值化利用，在固定床反应器中，进行木醋液催化重整制氢实验，采用浸渍法制备一系列不同Co添加量的Ni基催化剂，以产氢率、碳转化率、H₂选择性和积炭量为主要评价指标，探究液时空速、反应温度、镍钴比等工况对木醋液催化重整制氢的影响，同时采用 XRF、H₂-TPR、SEM及元素分析等方法对催化剂进行了表征。结果表明，液时空速增加，产气量增大，但液时空速过高会加速催化剂失活。高温有利于木醋液的催化重整制氢反应，温度到达900 ℃时，氢气产率最高。随着钴添加量的增加，反应产生的积炭降低，但氢气产率也会有所下降。因此，当液时空速为60 h⁻¹，温度为800 ℃时，采用Ni-0.5Co/Al₂O₃催化剂，最适于木醋液的催化重整制氢实验。
- 木醋液 /
- 重整制氢 /
- 镍基催化剂 /
- 积炭
Abstract: In order to realize high value utilization of wood vinegar, a series of Ni based catalysts with different Co contents prepared by impregnation method were tested in a fixed bed reactor. The effects of liquid space-time velocity, reaction temperature and Ni/Co ratio on hydrogen production, carbon conversion, H₂ selectivity and carbon deposition were investigated. The catalysts were characterized by XRF, H₂-TPR, SEM and elemental analysis. The results show that the gas production increases with the increase of space-time velocity of liquid, but the catalyst deactivation is accelerated when the space-time velocity of liquid is too high. High temperature is conducive to the catalytic reforming of wood vinegar to produce hydrogen. When the temperature reaches 900 °C, the hydrogen yield is the highest. With the increase of cobalt content, the carbon deposition and hydrogen yield decrease. Therefore, when the liquid space velocity is 60 h⁻¹ and the temperature is 800 °C, the Ni-0.5Co/Al₂O₃ catalyst is most conducive to the hydrogen production experiment of wood vinegar.
- wood vinegar /
- hydrogen from reforming /
- nickel-based catalyst /
- carbon deposition

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图 1 不同液时空速下各气体产率

Figure 1 Yields of gases at different LHSV

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图 2 不同液时空速下的碳转化率

Figure 2 Carbon conversion at different LHSV

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图 3 不同液时空速下的氢气选择性

Figure 3 H₂ selectivity at different LHSV

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图 4 不同温度下各气体产率

Figure 4 Yields of gases at different temperatures

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图 5 不同温度下的碳转化率

Figure 5 Carbon conversion at different temperatures

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图 6 不同温度下的氢气选择性

Figure 6 H₂ selectivity at different temperatures

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图 7 不同镍钴比催化剂的各气体产率

Figure 7 Yields of gases in catalysts with different Ni/CO ratios

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图 8 不同镍钴比催化剂的碳转化率

Figure 8 The carbon conversion in catalysts with different Ni/CO ratios

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图 9 不同镍钴比催化剂的氢气选择性

Figure 9 The H₂ selectivity in catalysts with different Ni/CO ratios

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图 10 催化剂的H₂-TPR谱图

Figure 10 H₂-TPR profiles of catalysts

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图 11 反应后催化剂的表观形貌照片

Figure 11 SEM images of used catalysts

(a): used Ni/Al₂O₃; (b): used Ni-0.5Co/Al₂O₃; (c): used Co/Al₂O₃

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图 12 不同液时空速、不同温度和不同镍钴比催化剂的含炭量

Figure 12 Carbon content of catalysts with different LHSV, temperatures and Ni/CO ratios

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图 13 GC-MS色谱图上各组分的总面积和数量

Figure 13 Total area and number of components in GC-MS chromatograms

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表 1 木醋液的主要成分统计

Table 1 Statistical result on the main components of wood vinegar

No	RT	Name	Mol.formula	Area/%
1	4.297	water	H₂O	23.95
2	4.958	acetic acid, methyl ester	C₃H₆O₂	1.73
3	7.474	acetic acid	C₂H₄O₂	16.63
4	8.496	2-propanone, 1-hydroxy-	C₃H₆O₂	6.71
5	10.026	propanoic acid	C₃H₆O₂	1.81
6	11.152	1-hydroxy-2-butanone	C₄H₈O₂	1.41
7	12.591	butanoic acid	C₄H₈O₂	0.54
8	13.05	3-cyclopentene-1-acetaldehyde, 2-oxo-	C₇H₈O₂	1.17
9	14.788	2-cyclopenten-1-one, 2-methyl-	C₆H₈O	0.68
10	17.849	2-cyclopenten-1-one, 3-methyl-	C₆H₈O	0.68
11	17.989	butyrolactone	C₄H₆O₂	0.98
12	19.532	2-cyclopenten-1-one, 2-hydroxy-3-methyl-	C₆H₈O₂	2.49
13	20.377	phenol	C₆H₆O	4.99
14	20.983	phenol, 2-methoxy-	C₇H₈O₂	1.54
15	21.797	phenol, 2-methyl-	C₇H₈O	0.94
16	22.28	nonane, 5-butyl-	C₁₃H₂₈	0.95
17	22.819	phenol, 4-methyl-	C₇H₈O	0.58
18	22.874	phenol, 3-methyl-	C₇H₈O	0.84
19	23.143	propanoic acid, 2-methyl-, anhydride	C₈H₁₄O₃	2.23
20	23.939	phenol, 2-methoxy-4-methyl-	C₈H₁₀O₂	0.84
21	24.196	cyclopropyl carbinol	C₄H₈O	5.77
22	26.393	3(2H)-furanone, dihydro-5-isopropyl-	C₇H₁₂O₂	0.95
23	27.214	1,4:3,6-dianhydro-α-D-glucopyranose	C₆H₈O₄	1.16
24	29.142	phenol, 2,6-dimethoxy-	C₈H₁₀O₃	2.07
25	31.419	phenol, 4-methoxy-3-(methoxymethyl)-	C₉H₁₂O₃	0.65
26	31.713	hydroquinone	C₆H₆O₂	0.71
27	37.087	1,6-anhydro-α-D-glucopyranose (levoglucosan)	C₆H₁₀O₅	4.04
note: only the components with relative peak area percentage greater than 0.5% were counted in the table

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表 2 催化剂的组成

Table 2 Component content of catalysts

Components	a	b	c	d	e
Ni/%	3.95	2.78	3.12	1.87	0.00
Co/ %	0.00	1.75	2.47	3.24	3.31

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表 3 木醋液催化重整制氢反应的实验方案

Table 3 Experimental scheme of hydrogen production by catalytic reforming of wood vinegar

Factors	Levels
LHSV/h⁻¹	10	20	30	40	50	60	70	80
Temperature/°C	500	600	700	800	900
Ni/Co ratio	1:0	1:0.5	1:1	0.5:1	0:1

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