生物质化学工程 ›› 2019, Vol. 53 ›› Issue (5): 49-56.doi: 10.3969/j.issn.1673-5854.2019.05.009
尹航1,2,徐卫1,2,孙云娟1,2,许玉1,2,应浩1,2,*(),宁思云1,2
收稿日期:
2018-07-09
出版日期:
2019-09-30
发布日期:
2019-09-27
通讯作者:
应浩
E-mail:hy2478@163.com
作者简介:
尹航(1994-),男,黑龙江哈尔滨人,本科,研究方向为生物质热化学转化技术
基金资助:
Hang YIN1,2,Wei XU1,2,Yunjuan SUN1,2,Yu XU1,2,Hao YING1,2,*(),Siyun NING1,2
Received:
2018-07-09
Online:
2019-09-30
Published:
2019-09-27
Contact:
Hao YING
E-mail:hy2478@163.com
Supported by:
摘要:
天然气因其清洁、高效、使用方便的特点而有着其他化石能源无法比拟的优势。随着天然气需求量的增加,天然气供需矛盾也逐渐凸显,生物质合成气催化制取合成天然气成为解决天然气供需矛盾的技术之一。针对生物质合成气甲烷化过程中存在的问题,从反应过程、催化剂、反应器等方面阐述了生物质合成气甲烷化研究现状;对比了不同催化剂的催化性能,分析得出Ni基催化剂是最适合工业化的甲烷化催化剂之一。列举了国外一些固定床和流化床甲烷化反应器工业化的案例,分析了其各自的生产工艺及优缺点,得出流化床是甲烷化反应器中较为有前景的反应器,并对生物质合成气催化制取合成天然气技术的发展方向进行了展望。
中图分类号:
尹航,徐卫,孙云娟,许玉,应浩,宁思云. 生物质合成气催化甲烷化技术研究进展[J]. 生物质化学工程, 2019, 53(5): 49-56.
Hang YIN,Wei XU,Yunjuan SUN,Yu XU,Hao YING,Siyun NING. Research Advances in Catalytic Methanation of Bio-syngas[J]. Biomass Chemical Engineering, 2019, 53(5): 49-56.
表1
近年CO甲烷化催化剂研究进展1)"
催化剂 catalyst | 制备方法 preparation method | 活性组分/% active component | 温度/℃ temperature | 压力/MPa pressure | CO转化率/% CO conversion | CH4选择率/% CH4 selectivity | 测试时长/h stability test time | 参考文献 reference |
Ni- α-Al2O3 | I | 10 | 450 | 0.1 | 96.0 | 90.0 | 50 | [ |
Ni-Al2O3 | CP | 15 | 400 | 0.1 | 98.2 | 84.7 | 120 | [ |
Ni/MCM-41 | HT | 10 | 350 | 0.1 | 97.9 | 88.2 | 100 | [ |
Ni/MWNTs | I | 13 | 350 | 0.1 | 95.0 | 85.0 | 240 | [ |
Ni-membrane | I | 99.9 | 350 | 0.2 | 95.0 | 96.0 | — | [ |
Ni-SBA-15 | pH | 3.6 | 350 | 0.3 | 100.0 | 98.6 | 100 | [ |
Ni/CeO2-Al2O3 | I | 10 | 350 | — | — | 80.0 | — | [ |
Ni-Fe/Al2O3 | I | 15 | 262 | 0.1 | 95.0 | 90.0 | 24 | [ |
Ni-SBA-16-NH2 | I | 10 | 350 | 0.3 | 100.0 | 99.9 | 100 | [ |
Ni-AlOOH-Al2O3 | I | 28 | 550 | 0.3 | 98.0 | 92.0 | — | [ |
Co3O4 | CP | — | 300 | 2.0 | 100.0 | — | — | [ |
Ru/ABC | I | 0.3 | 350 | — | 97.0 | 92.0 | — | [ |
Si-Ni/SiO2 | SI | 20 | 350 | 0.1 | 70.0 | 60.0 | 42 | [ |
表2
近年CO2甲烷化催化剂研究进展"
催化剂 catalyst | 制备方法1) preparation method | 活性组分/% active component | 温度/℃ temperature | 压力/MPa pressure | CO2转化率/% CO2 conversion | CH4选择率/% CH4 selectivity | 测试时长/h stability test time | 参考文献 reference |
Ni/MCM-41 | HT | 10 | 400 | 0.1 | 56.5 | 96.0 | — | [ |
Ni-CeO2 | I | 5 | 300 | 0.1 | 55.0 | 100.0 | — | [ |
Ni/ γ-Al2O3 | I | 3 | 350 | 0.1 | 83.6 | 100.0 | 10 | [ |
Ni/MSN | I | 15 | 300 | 0.1 | 64.1 | 99.9 | 200 | [ |
Ni-TiO2 | CP | 5 | 218 | 0.1 | 96.0 | 99.0 | — | [ |
Ni/CeO2-ZrO3 | SG | 20 | 350 | 0.1 | 79.7 | 97.3 | 90 | [ |
Co/KIT-6 | I | 0.8 | 260 | 0.1 | 48.9 | 100.0 | — | [ |
Ru-TiO2 | BS | 20 | 180 | 0.1 | — | 100.0 | 170 | [ |
Ru/ γ-Al2O3 | I | 3 | 350 | 0.1 | 85.0 | 85.0 | 2 | [ |
图3
居辛1MW合成天然气装置[60] 1.气化反应器gasifier; 2.过滤器filter; 3.焦油/噻吩脱除塔tar/thiophene removal tower; 4.压缩机compressor; 5.硫化氢初脱塔bulk H2S removal tower; 6.预热器preheater; 7.硫化氢终脱塔final H2S removal tower; 8.氢气分离塔H2 removal tower; 9.CO2脱除塔CO2 removal tower; 10.压缩机compressor; 11.水蒸气脱除塔H2O removal tower; 12.氨气脱除塔NH3 removal tower; 13.余热回收器heat recovery; 14.流化床甲烷化反应器fluidised bed methanation reactor "
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