生物质焦油重整催化剂的研究进展

doi:10.3969/j.issn.1673-5854.2020.06.011

摘要/Abstract

摘要：

生物质热解制备富氢合成气是当前的研究热点，催化重整生物质焦油不仅能够有效地去除焦油，而且可以增加气相中H₂和CO的含量。本文综述了近几年关于生物质焦油重整催化剂的研究，讨论了镍基催化剂、非镍过渡金属催化剂和碱金属催化剂的优劣势。镍基催化剂使用时通常需要载体，虽然具有较高的催化活性，但是易通过积炭和镍烧结而失活。非镍过渡金属催化剂中的贵金属催化剂虽然具有极高的活性和稳定性，但是价格昂贵。碱金属催化剂易挥发而永久失活。

关键词: 生物质, 热解, 焦油重整, 催化剂

Abstract:

The preparation of hydrogen-rich syngas by biomass pyrolysis is a popular research. Catalytic reforming of biomass tar can not only effectively remove tar, but also increase the content of H₂ and CO in the gas phase. In this paper, the research on biomass tar reforming catalysts in recent years was reviewed. The advantages and disadvantages of nickel-based catalysts, non-nickel transition metal catalysts and alkali metal catalysts were discussed. Nickel-based catalysts usually require the support when they are used. Although they have high catalytic activity, they are easily deactivated by carbon deposition and nickel sintering. Although precious metal catalysts in non-nickel transition metal catalysts have extremely high activity and stability, but they are expensive, and other non-nickel metal catalysts have lower activity than nickel-based catalysts. The alkali metal catalysts are volatile and permanently inactivated.

Key words: biomass, pyrolysis, tar reforming, catalyst

中图分类号:

TQ35
TQ524

尚双, 兰奎, 王艳, 张娟娟, 秦振华, 李建芬. 生物质焦油重整催化剂的研究进展[J]. 生物质化学工程, 2020, 54(6): 65-73.

Shuang SHANG, Kui LAN, Yan WANG, Juanjuan ZHANG, Zhenhua QIN, Jianfen LI. Research Progress on Catalyst for Tar Reforming in Biomass Gasification[J]. Biomass Chemical Engineering, 2020, 54(6): 65-73.

图/表 2

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表2

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催化剂类型 catalyst type	代表性催化剂 representative catalyst	性质 properties	文献 reference
Ni基催化剂 Ni-based catalyst	金属氧化物载体 metal oxide support	抗积炭能力差，易失活 easy deactivation due to low resistance ability on coke formation	^{[23, 35]}
	天然矿石载体 natural ore support	廉价且丰富，催化活性相对低 inexpensive and abundant, relatively low catalytic activity	^[33-35]
	分子筛载体 zeolite support	比表面积大，催化活性高，合成成本高 high specific surface area, high catalytic activity and high synthesis cost	^[37-40]
	炭载体 char support	价廉且丰富，多孔，具有吸附焦油和催化裂解焦油双重功能 inexpensive and abundant, rich pore structure, adsorption and catalytic cracking of tar	^[43-46]
非镍过渡金属催化剂 non-nickel transition metal catalyst	Rh/Ce_0.14Zr_0.81Mg_0.05O₂, Ru/12SrO-7Al₂O₃	高催化活性和稳定性，合成成本高 high catalytic activity and stability, high synthesis cost	^[48-49]
碱金属催化剂 alkali metals catalyst	稻壳炭，K rice husk char, K	减少灰分问题，高温下挥发而失活 reduce ashhandling issues and volatilization at high temperature	^[52-54]

催化剂¹⁾ catalyst	原料 feedstock	温度/ ℃ temp.	焦油转化率/% tar conversion	测试时长/min test time	文献 reference
12%NiO/γ-Al₂O₃	稻壳rice husk	800	99.99	—	^[23]
11%Ni/MgO	苯酚phenol	450	83.1	360	^[25]
20%Ni/Al₂O₃	愈创木酚guaiacol	600	90	300	^[37]
20%Ni/SBA-15	愈创木酚guaiacol	600	65	300	^[37]
8%Fe-6%Ni/PG	稻壳焦油rice husk tar	700	99.9	—	^[30]
12%Ni/Al₂O₃	稻秆焦油rice straw tar	650	54.2	—	^[31]
12%Ni-3%Co/Al₂O₃	稻秆焦油rice straw tar	650	59.0	—	^[31]
15%Co/Al₂O₃	稻秆焦油rice straw tar	650	81.4	—	^[31]
5%Ni/橄榄石olivine	甲苯toluene	800	97	1680	^[34]
6%Ni-2%MgO/HZSM-5	稻壳焦油rice husk tar	800	91.03	—	^[39]
Ni-Fe/RHC	稻壳rice husk	800	86	—	^[43]
Ni-6/焦炭char	松木屑pine sawdust	800	83	—	^[45]
1.5K-焦炭char	玉米芯corncob	700	95.8	—	^[54]

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