Research on the preparation of Fischer-Tropsch synthesis gas by biomass carbonization pyrolysis gas catalytic reforming

doi:10.16085/j.issn.1000-6613.2019-1183

Abstract

Abstract: Biomass pyrolysis gas is a kind of high calorific value combustible gas, which has important development and utilization value. However, due to its complex components, multi-tar oil, CO₂, CH₄ and other components have tremendous hazard to pyrolysis gasification process and related equipment. and the viscous liquid formed by condensation is likely to cause blockage of the pipeline, and the carbon black generated by direct combustion will cause environmental pollution, all of which constitutes a major factor restricting the further development and utilization of pyrolysis gas. This paper analyzes the feasibility of pyrolysis gas catalytic reforming to Fischer-Tropsch synthesis gas. It introduces respectively the research status of continuous and segmented pyrolysis-catalytic reforming equipment, nickel-based, calcium-based, iron-based, alkali-based, carbon and other catalysts as well as pyrolysis gas separation and purification technology, analyzes the existing problems in current research in terms of non-uniformity of catalytic reforming equipment, lack of relevant industry standards, different catalysts and catalytic reforming effect as well as unclear mechanism of catalyst additives, proposes the future research direction such as the application of segmented pyrolysis-catalytic reforming equipment and using biochar as catalytic reforming catalyst, opens up a new way of development and utilization of biomass carbonization pyrolysis gas.

Key words: biomass, carbonization, pyrolysis gas, tar, catalytic reforming, Fischer-Tropsch synthesis gas

摘要： 生物质热解气是一种高热值的可燃气体，具有重要的开发利用价值，但由于其复杂的组分，多焦油和CO₂、CH₄等成分对热解气化过程以及相关的设备都有较大的危害，而冷凝下来形成的黏稠液体易造成管道堵塞，直接燃用产生的炭黑会造成环境污染，成为制约热解气进一步开发利用的主要因素。本文分析了热解气催化重整制取费-托合成气的可行性，分别介绍了连续和分段式热解-催化重整设备，镍基、钙基、铁基、碱金属类、生物炭等催化剂，以及热解气分离提纯技术等方面的研究现状，分析了目前热解气制取费-托合成气研究中存在的催化重整设备规格不统一、缺乏相关的行业标准、不同催化剂与催化剂助剂的催化重整效果、机理尚不明确等问题，并提出了采用分段式热解-催化重整设备，并以炭化产品生物炭作为催化重整催化剂的未来研究方向，开辟了生物质炭化热解气开发利用的新途径。

关键词: 生物质, 炭化, 热解气, 焦油, 催化重整, 费-托合成气

CLC Number:

YUAN Yanwen, ZHAO Lixin, MENG Haibo, CONG Hongbin, HUO Lili, TANG Sen. Research on the preparation of Fischer-Tropsch synthesis gas by biomass carbonization pyrolysis gas catalytic reforming[J]. Chemical Industry and Engineering Progress, 2019, 38(s1): 152-158.

袁艳文, 赵立欣, 孟海波, 丛宏斌, 霍丽丽, 汤森. 生物质炭化热解气催化重整制取费-托合成气研究进展[J]. 化工进展, 2019, 38(s1): 152-158.

References

[1] 姚宗路, 仉利, 赵立欣, 等. 生物质热解气燃烧装置设计与燃烧特性试验[J]. 农业机械学报, 2017, 48(12):299-305. YAO Z L, ZHANG L, ZHAO L X, et al. Gas burner design and experiment on emission characteristics of biomass pyrolysis gas[J]. Transactions of the Chinese Society of Agricultural Machinery, 2017, 48(12):299-305.
[2] 陈雨亭, 王燕刚, 秦恒飞, 等. 基于对生物质焦油催化裂解的催化材料[J]. 广州化工, 2015, 43(13):4-7. CHEN Y L, WANG Y G, QIN H F, et al. Catalytic materials based on the catalytic cracking of biomass tar[J]. Guangzhou Chemical Industry, 2015, 43(13):4-7.
[3] 周立进, 王磊, 黄慧慧, 等. 费托合成工艺研究进展[J]. 石油化工, 2012, 41(12):1429-1435. ZHOU L J, WANG L, HUANG H H, et al. Research progresses in Fischer-Tropsch synthesis process[J]. Petrochemical Technology, 2012, 43(12):1429-1435.
[4] 齐景丽, 吕秀荣. 利用炼油厂干气制取费-托合成气的可行性探讨[J]. 炼油与化工, 2012, 23(5):1-3. QI J L, LÜ X R. Feasibility of using refinery dry gas to produce F-Tsyngas[J]. Refining and Chemical Industry, 2012, 23(5):1-3.
[5] 林伟钢, 宋文立. 丹麦生物质发电的现状和研究发展趋势[J]. 燃料化学学报, 2001, 29(6):650-655. LIN W G, SONG W L. Power production from biomass in Denmark[J]. Journal of Fuel Chemistry and Technology, 2001, 29(6):650-655.
[6] 汪俊峰, 常杰, 阴秀丽, 等. 生物质催化合成甲醇的研究[J]. 燃料化学学报, 2005, 33(1):58-61. WANG J F, CHANG J, YIN X L, et al. Catalytic synthesis of methanol from biomass-derived syngas[J]. Journal of Fuel Chemistry and Technology, 2005, 33(1):58-61.
[7] 赵先国, 常杰, 吕鹏梅, 等. 生物质流化床富氧气化的实验研究[J]. 燃料化学学报, 2005, 33(2):199-204. ZHAO X G, CHANG J, LÜ P M, et al. Biomass gasification under O₂-rich gas in a fluidized bed reactor[J]. Journal of Fuel Chemistry and Technology, 2005, 33(2):199-204.
[8] YAN Z, BUKUR D B, GOODMAN D W. Silica-supported rhodium-cobalt catalysts for Fischer-Tropsch synthesis[J]. Catalysis Today, 2011, 160:39-43.
[9] ALI S, MOHB ZZBIDI N A, SUBBARAO D. Correlation between Fischer-Tropsch catalytic activity and composition of catalysts[J]. Chemistry Central Journal, 2010, 5(1):68.
[10] 杨延涛, 雷廷宙, 徐海燕, 等. 生物质裂解气的催化重整调变特性研究[J]. 河南科学, 2016, 34(6):1678-1681. YANG Y T, LEI T Z, XU H Y, et al. Catalytic reforming and adjustment of biomass fuel gas[J]. Henan Science, 2016, 34(6):1678-1681.
[11] OIKE T, KUDO S, YANG H, et al. Sequential pyrolysis and potassium-catalyzed steam-oxygen gasification of woody biomass in a continuous two-stage reactor[J]. Energy & Fuels, 2014, 28(10):6407-6418.
[12] BRANDT P, LARSEN E, HENRIKSEN U. High tar reduction in a two-stage gasifier[J]. Energy & Fuels, 2000, 14(4):816-819.
[13] ELIZABETH Gusta, AJAY K Dalai, MD Azhar Uddin, et al. Catalytic decomposition of biomass tars with dolomites[J]. Energy & Fuels, 2009, 23(4):2264-2272.
[14] 王敬茹, 马腾, 丛宏斌, 等. 生物质热解气重整试验平台设计与试验[J]. 可再生能源, 2019, 37(4):482-487. WANG J R, MA T, CONG H B, et al. Design and experimental test for a biomass pyrolysis gas reforming reactor[J]. Renewable Energy Resources, 2019, 37(4):482-487.
[15] 杨建成, 张光义, 许光文, 等. 秸秆热解-页岩灰催化裂解生产低焦油生物合成气[J]. 化工学报, 2017, 68(10):3779-3787. YANG J C, ZHANG G Y, XU G W, et al. Bio-syngas production with low tar content from sorghum straw by pyrolysis and catalytic cracking with oil shale ash[J]. CIESC Journal, 2017, 68(10):3779-3787.
[16] CORELLA J, AZNAR M P, DELGADO J, et al. Steam gasification of cellulosic wastes in a fluidized bed with down-stream vessels[J]. Industrial& Engineering Chemistry Research, 1991, 30(10):2252-2262.
[17] AZNAR M P, CORELLA J, DELGADO J. Improved steam gasification of lignocellulosic residues in a fluidized bed with commercial steam reforming catalysts[J]. Industrial & Engineering Chemistry Research, 1993, 32(1):1-10.
[18] BAKER E G, MUDGE L K, BROWN M D. Steam gasification of biomass with nickel secondary catalysts[J]. Industrial & Engineering Chemistry Research, 1987, 26(1):1335-1339.
[19] NARVAEZ I, CORELLA J, ORIO A. Fresh tar elimination over a commercial steam reforming catalyst[J]. Industrial & Engineering Chemistry Research, 1997, 36(2):317-327.
[20] 王铁军, 常杰, 吴创之, 等. 生物质气化焦油催化裂解特性[J]. 太阳能学报, 2003, 24(3):376-379. WANG T J, CHANG J, WU C Z, et al. Performance of catalytic cracking of biomass tar[J]. Acta Energiae Solaris Sinica, 2003, 24(3):376-379.
[21] VASSILATOS V, TARALLAS G, SIOSTROM K, et al. Catalytic cracking of tar in biomass pyrolysis gas in the presence of calcined dolomite[J]. Industrial & Engineering Chemistry Research, 1992, 70(10):1008-1013.
[22] OLIVARES A, AZNAR M P, CABALLERO M A, et al. Produced gas upgrading by in-bed use of dolomite[J]. Industrial & Engineering Chemistry Research, 1997, 36(10):5220-5226.
[23] SIMELL P A. Catalytic purification of tarry fuel gas[J]. Fuel, 1990, 71(10):1218-1225.
[24] 米铁, 吴正舜, 余新明, 等. CaO催化裂解生物质气化焦油实验研究[J]. 太阳能学报, 2011, 32(5):724-729. MI T, WU Z S, YU X M, et al. The experimental study on biomass tar-cracking by CaO catalyst[J]. Acta Energiae Solaris Sinica, 2011, 32(5):724-729.
[25] 陈鸿伟, 王晋权, 庞永梅, 等. 玉米秸秆催化热解试验研究[J]. 可再生能源, 2007, 25(5):19-22. CHEN H W, WANG J Q, PANG Y M, et al. Experimental study of catalytic pyrolysis of corn stalk[J]. Renewable Energy Resources, 2007, 25(5):19-22.
[26] HU G, XU S, LI S, et al. Steam gasification of apricot stones with olivine and dolomite as downstream catalysts[J]. Fuel Processing Technology, 2006, 87(5):375-382.
[27] 周劲松, 王铁柱, 骆仲泱, 等. 生物质焦油的催化裂解研究[J]. 燃料化学学报, 2003, 31(2):144-48. ZHOU J S, WANG T Z, LUO Z Y, et al. Catalytic cracking of biomass tar[J]. Journal of Fuel Chemistry and Technology, 2003, 31(2):144-148.
[28] PONZIO A, KALISZ S, BLASIAK W. Effect of operating conditions on tar and gas composition in high temperature air/steam gasification (HTAG)of plastic containing waste[J]. Fuel Processing Technology, 2006, 87(3):223-233.
[29] NORDGREEN T, NEMANOVA V, E NGVALL K, et al. Iron-based materials as tar depletion catalysts in biomass gasification:dependency on oxygen potential[J]. Fuel, 2012, 95:71-78.
[30] SIMELL P A, LEPPALAHTI J K, BREDENBERG J B. Catalytic purification of tarry fuel gas with carbonate rocks and ferrous materials[J]. Fuel, 1992, 71(2):211-218.
[31] LIU H, CHEN T, CHANG D, et al. Catalytic cracking of tar derived from rice hull gasification over palygorskite-supported Fe and Ni[J]. Journal of Molecular Catalysis A:Chemical, 2012, 363:304-310.
[32] LIU H, CHEN T, CHANG D, et al. Effect of preparation method of palygorskite-supported Fe and Ni catalysts on catalytic cracking of biomass tar[J]. Chemical Engineering Journal, 2012, 188:108-112.
[33] 刘海波, 陈天虎, 张先龙, 等. 助剂对镍基催化剂催化裂解生物质气化焦油性能的影响[J]. 催化学报, 2010, 31(4):409-414. LIU H B, CHEN T H, ZHANG X L, et al. Effect of additives on catalytic cracking of biomass gasification tar over Nickel-based catalyst[J]. Chinese Journal of Catalysis, 2010, 31(4):409-414.
[34] HUANG B S, CHEN H Y, CHUANG K H, et al. Hydrogen production by biomass gasification in a fluidized-bed reactor promoted by an Fe/CaO catalyst[J]. International Journal of Hydrogen Energy, 2012, 37(8):6511-6518.
[35] 陈鸿伟, 张志远, 翟建军, 等. 碱/碱土金属对煤热解影响的研究进展[J]. 热力发电, 2017, 46(1):1-6. CHEN H W, ZHANG Z Y, ZHAI J J, et al. Effects of alkali/alkaline earth metals on coal pyrolysis:research progress[J]. Thermal Power Generation, 2017, 46(1):1-6.
[36] LI C Z, SATHE C, KERSHAW J R, et al. Fates and roles of alkali and alkaline earth metals during the py-rolysis of a Victorian brown coal[J]. Fuel, 2000, 79(3):427-438.
[37] 谭洪, 王树荣, 骆仲泱, 等. 金属盐对生物质热解特性影响试验研究[J]. 工程热物理学报, 2005, 26(5):742-744. TAN H, WANG S R, LUO Z Y, et al. Influence of metallic salt on biomass flash pyrolysis characteristics[J]. Journal of Engineering Thermophysics, 2005, 26(5):742-744.
[38] ENCINAR J M, BELTRAN F J, RAMIRO A. Pyrolysis/gasification of agricultural residues by carbon dioxide in the presence of different additives:influence of variables[J]. Fuel Processing Technology, 1998, 55(3):219-233.
[39] GUAN G, KAEWPANHA M, HAO X, et al. Promoting effect of potassium addition to calcined scallop shell supported catalysts for the decomposition of tar derived from different biomass resources[J]. Fuel, 2013, 109:241-247.
[40] GUAN G, KAEWPANHA M, HAO X, et al. Steam reforming of tar derived from lignin over pompom-like potassium-promoted iron-based catalysts formed on calcined scallop shell[J]. Bioresource Technology, 2013, 139:280-284.
[41] AZNAR M P. Commercial steam reforming catalysts to improve biomass gasification with steam-oxygen mixture catalytic tar removal[J]. Industrial & Engineering Chemistry Research, 1998, 37(1):2668-2680.
[42] 王磊, 吴创之, 赵增立, 等. 热解焦对生物质焦油催化裂解的影响[J]. 太阳能学报, 2006, 27(5):514-518. WANG L, WU C Z, ZHAO Z L, et al. Effect of char on catalytic cracking of tar from biomass gasification gas with toluene as a model compound[J]. Acta Energiae Solaris Sinica, 2006, 27(5):514-518.
[43] 尤占平, 由世俊, 李宪莉, 等. 生物质炭催化裂解焦油的实验研究[J]. 太阳能学报, 2011, 32(5):718-723. YOU Z P, YOU S J, LI X L, et al. Experimental research on tar catalytic cracking over biomass char[J]. Acta Energiae Solaris Sinica, 2011, 32(5):718-723.
[44] 孟凡彬, 孟军. 玉米秸秆炭和木屑炭催化裂解焦油的试验研究[J]. 沈阳农业大学学报, 2017, 48(4):472-476. MENG F B, MENG J. Experimental study on catalytic cracking of tar with corn stalk charcoal and sawdust char coal[J]. Journal of Shenyang Agricultural University, 2017, 48(4):472-476.
[45] 廖恒易. 气体分离提纯应用变压吸附技术的分析[J]. 科技视界, 2016, 20(7):23-24. LIAO H Y. Analysis of gas pressure separation and application of pressure swing adsorption technology[J]. Science & Technology Vision, 2016, 20(7):23-24.
[46] 张沛生. 重油催化裂化干气氢提纯技术的开发[J]. 炼油设计, 1998, 28(3):8-10. ZHANH P S. Development of purification technology of hydrogen from RFCC dry gas[J]. Refining Design, 1998, 28(3):8-10.
[47] 纪志愿. 氢提纯工艺的选择及其工业应用[J]. 炼油设计, 1998, 28(6):46-50. JI Z Y. Selection of hydrogen purification process and its commercial application[J]. Refining Design, 1998, 28(6):46-50.
[48] 陈昱琪. 膜分离CO₂技术进展研究[J]. 现代商贸工业, 2019, 18(9):187-188. CHEN Y Q. Progress in membrane separation of CO₂[J]. Modern Trade Industry, 2019, 18(9):187-188.
[49] 黄晓磊, 吴旭飞, 宋新巍. 膜分离技术在气体分离纯化中的应用[J]. 化学推进剂与高分子材料, 2018, 16(6):23-28. HUANG X L, WU X F, SONG X W. Application of membrane separation technique in gas separation and purification[J]. Chemical Propellants & Polymeric Materials, 2018, 16(6):23-28.
[50] 李红伟, 邓迪, 史宇科, 等. 膜分离法油气回收现状分析与对策[J]. 石油化工腐蚀与防护, 2017, 34(2):25-29. LI H W, DENG D, SHI Y K, et al. Status quo analysis and suggestions for gasoline vapor recovery by membrane separation method[J]. Corrosion & Protection in Petro Chemical Industry, 2017, 34(2):25-29.