改性橄榄石对C7H8/CO2催化重整的影响

孟俊光; 王小波; 赵增立; 郑安庆; 李海滨

改性橄榄石对C₇H₈/CO₂催化重整的影响

孟俊光^{1, 2},
王小波^1, ,,
赵增立¹,
郑安庆¹,
李海滨¹

1.
中国科学院广州能源研究所中国科学院可再生能源重点实验室, 广东广州 510640
2.
中国科学院大学, 北京 100049

基金项目:

国家自然科学基金 51506208

国家自然科学基金国际（地区）合作与交流项目 51661145011

详细信息

通讯作者:
王小波, E-mail:wangxb@ms.giec.ac.cn

中图分类号: TK6
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- 文章访问数: 94
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- 被引次数: 0
出版历程
- 收稿日期: 2016-11-14
- 修回日期: 2017-01-06
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-03-10

Effects of modified olivine on the CO₂ reforming of toluene

1.
The Key Laboratory of Renewable Energy of Chinese Academy of Sciences, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Funds:

the National Natural Science Foundation of China 51506208

the Projects of International Cooperation and Exchanges NSFC 51661145011

摘要

摘要: 在固定床反应器中，以甲苯作为生物质气化焦油模型化合物，橄榄石作为甲苯裂解催化剂，结合XRD、SEM、BET、H₂-TPR等表征手段，考察了不同重整反应温度、CO₂浓度、橄榄石煅烧温度以及载镍量对甲苯催化重整性能的影响。结果表明，甲苯转化率随着重整反应温度的升高而增加，橄榄石对甲苯具有较高的催化活性，经900℃煅烧后的橄榄石活性最高。相比于橄榄石直接催化裂解甲苯，CO₂的加入能够显著降低催化剂表面的积炭率，当CO₂/C₇H₈物质的量比为4时，橄榄石催化剂表面的积炭率降低至17.0%。橄榄石载镍后，对C₇H₈/CO₂的催化重整性能进一步提高，甲苯转化率最高达到99.4%，但是积炭率也会随之增加。
- 改性橄榄石 /
- 甲苯 /
- 二氧化碳 /
- 催化重整
Abstract: An olivine catalyst was tested in a fixed bed reactor in CO₂ reforming of the toluene as a tar model molecule produced during biomass gasification. The olivine catalyst was characterized by XRD, SEM, BET, H₂-TPR; and the effects of the operating parameters (reforming reaction temperature and CO₂ concentration) and catalyst preparation parameters (calcination temperature and nickel content) on the activity and selectivity for toluene conversion were examined. The results show that the olivine catalyst can increase the toluene conversion and lower the carbon formation. The toluene conversion also increases with the reforming temperature rise. The calcined olivine reaches the highest activity when the calcination temperature is 900℃. The CO₂ addition can reduce the carbon formation obviously by 17.0% when the CO₂/C₇H₈ molar ratio is 4. Moreover, the Ni/olivine catalyst has a better performance and the toluene conversation is up to 99.4%, while the carbon formation increases a little bit.
- modified olivine /
- toluene /
- CO₂ /
- catalytic reforming

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图 1 C₇H₈/CO₂催化重整装置示意图

Figure 1 Experimental scheme of C₇H₈/CO₂ reforming

1, 2, 3, 4: mass flowmeter; 5: metering pump; 6: quartz reactor; 7: catalyst; 8: furnace; 9: thermocouple; 10: condenser; 11: isopropanol

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图 2 不同煅烧温度下橄榄石的XRD谱图

Figure 2 XRD patterns of olivine calcined at different temperatures

◆ : MgFe₂O₄; ■ : Mg₂SiO₄; ▲ : MgSiO₃; ▼ : Mg₃Si₂O₅(OH)₄; □ : FeSiO₃; ○ : Fe₂O₃; ● : (Mg, Fe)₂SiO₄; ◀ : (Mg, Fe) SiO₃; △ : Mg_0.3Fe_0.7SiO₃

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图 3 不同煅烧温度下橄榄石的SEM照片

Figure 3 SEM images of olivine calcined at different temperatures

(a): raw ore; (b): olivine-700 ℃; (c): olivine-900 ℃; (d): olivine-1 100 ℃; (e): olivine-1 400 ℃

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图 4 不同温度煅烧橄榄石的H₂-TPR谱图

Figure 4 H₂-TPR profiles of olivine calcined at different temperatures

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图 5 甲苯裂解反应路径示意图^[15]

Figure 5 Schematic diagram of toluene pyrolysis reaction paths

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图 6 重整反应温度对C₇H₈/CO₂催化重整的影响

Figure 6 Effects of reforming reaction temperature on C₇H₈/ CO₂ reforming

(CO₂/C₇H₈(molar ratio)=3)

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图 7 CO₂/C₇H₈物质的量比对C₇H₈/CO₂催化重整的影响

Figure 7 Effects of CO₂/C₇H₈ molar ratio on C₇H₈/ CO₂ reforming

(bed material: olivine-900 ℃-5 h, reforming reaction temperature: 850 ℃)

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图 8 载镍量对C₇H₈/CO₂催化重整的影响

Figure 8 Effects of Ni loading on C₇H₈/ CO₂ reforming

(bed material: olivine-900 ℃-5 h, reforming reaction temperature: 850 ℃, CO₂/C₇H₈(molar ratio)=4)

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图 9 煅烧温度对C₇H₈/CO₂催化重整的影响

Figure 9 Effects of calcination temperature on C₇H₈/ CO₂ reforming

(bed material: olivine/olivine-4%Ni, reforming reaction temperature: 850 ℃, CO₂/C₇H₈(molar ratio)=4)

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表 1 橄榄石原矿的化学组成

Table 1 Chemical compositions of natural olivine

Content w/%
Fe	Mg	Ni	Al	Si	O	Ca	Cr	Mn
5.52	23.39	0.22	1.91	17.72	49.43	1.17	0.28	0.11

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表 2 不同煅烧温度下橄榄石的比表面积和平均孔径

Table 2 Surface area and average pore diameter of natural olivine and the olivine calcined at different temperatures

Sample	Surface area A/(m²·g^-1)	Average pore diameter d/nm
Raw ore	11.84	7.51
Olivine-700 ℃	39.86	7.99
Olivine-900 ℃	16.81	17.96
Olivine-1 100 ℃	4.56	25.73
Olivine-1 400 ℃	1.67	10.63

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