秸秆热解-页岩灰催化裂解生产低焦油生物合成气

doi:10.11949/j.issn.0438-1157.20170370

摘要/Abstract

摘要：

为从高粱秸秆生产高品质、低焦油含量生物合成气，基于其单段热解特性研究，借助两段式固定床反应器实施两段热解（热解+裂解），同时考察页岩灰对热解挥发分的催化裂解效果。结果表明：相对单段热解，两段热解强化了水蒸气与挥发分（尤其是与热解气）的交互；提高裂解温度促进焦油裂解和重整，便利了热解气的生成，同时提高合成气（H₂+CO）的产率和H₂/CO体积比；裂解中加入页岩灰显著促进生物焦油气化，大幅降低气体产物焦油含量：裂解温度适中（约850℃）时（450℃热解），热解气产率超过40%（质量），焦油产率低于1.0%（质量），合成气产量约186 ml·g^-1、体积分数高达64%，且H₂/CO比超过0.5。页岩灰便利H₂的生成，主要源于其铁组分对水气变换的催化作用。

关键词: 热解, 裂解, 高粱秸秆, 合成气, 页岩灰

Abstract:

To obtain high-quality bio-syngas with low tar content from sorghum straw,two-stage prolysis (prolysis+cracking) was performed in a two-stage fixed bed reactor based on the research on its one-stage prolysis characteristics,and the catalytic effects of oil shale ash on cracking the volatile products from pyrolysis were investigated.The results showed that compared to the one-stage prolysis,the two-stage prolysis strengthened the correlation between water vapor with volatiles (above all pyrolysis gas).High cracking temperatures facilitated cracking and reforming of tar,resulting in generation of more gas products and also enhancements in the bio-syngas (H₂+CO) yield and the H₂/CO volumetric ratio.The oil shale ash significantly promoted gasification of tar.With the oil shale ash added for cracking volatiles at the moderate temperature of 850℃(pyrolysis at 450℃),the gas yield surpassed 40%(mass) with such a low tar yield as 1.0%(mass).Meanwhile,the yield of bio-syngas reached up to 186 ml·g^-1 with its highest content of 64%(vol) in gas products,and the H₂/CO volumetric ratio was above 0.5.The oil shale ash facilitated H₂ generation mainly due to its ferric component capable of catalyzing water-gas shift reaction.

Key words: pyrolysis, cracking, sorghum straw, syngas, oil shale ash

中图分类号:

X789

杨建成, 张光义, 许光文, 文利雄. 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 Jiancheng, ZHANG Guangyi, XU Guangwen, WEN Lixiong. 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.

参考文献 33

[1]	LIU Z, WANG D, NING T, et al. Sustainability assessment of straw utilization circulation modes based on the emergetic ecological footprint[J]. Ecological Indicators, 2017, 75:1-7.
[2]	冯伟, 张利群, 庞中伟, 等. 中国秸秆废弃焚烧与资源化利用的经济与环境分析[J]. 中国农学通报, 2011, (6):350-354. FENG W, ZHANG L Q, PANG Z W, et al. The economic and environmental analysis of crop residues burning and reutilization in China[J]. Chinese Agricultural Science Bulletin, 2011, (6):350-354.
[3]	FENG W, ZHANG L Q, HE L J, et al. A mode research of straw recycling based on circular agriculture theory[J]. Agricultural Science & Technology-Hunan, 2011, 12(12):1921-1924.
[4]	吴创之, 马隆龙. 生物质能现化化利用技术[M]. 北京:化学工业出版社, 2003:197-201. WU C Z, MA L L. Modern Utilization Technology of Biomass Energy[M]. Beijing:Chemical Industry Process, 2003:197-201.
[5]	AHRENFELDT J, EGSGAARD H, STELTE W, et al. The influence of partial oxidation mechanisms on tar destruction in two stage biomass gasification[J]. Fuel, 2013, 112:662-680.
[6]	武景丽, 汪丛伟, 阴秀丽, 等. 基于TG-FTIR的生物油重质组分热解特性研究[J]. 太阳能学报, 2010, 31(1):113-117. WU J L, WANG C W, YIN X L, et al. Study on pyrolysis of heavy by using TG-FTIR fractions of bio-oil[J]. Acta Energiae Solaris Sinica, 2010, 31(1):113-117.
[7]	吕微, 张琦, 王铁军, 等. 生物油重质组分模型物热解行为及其动力学研究[J]. 燃料化学学报, 2013, (2):198-206. LÜ W, ZHANG Q, WANG T J, et al. Thermal degradation behaviors and pyrolysis kinetics of model compounds of bio-oil heavy fractions[J]. Journal of Fuel Chemistry and Technology, 2013, (2):198-206.
[8]	张摇怡, 陈登宇, 张摇栋, 等. 生物油TG-FTIR分析与热解气化特性研究[J]. 燃料化学学报, 2012, (10):1194-1199. ZHANG Y Y, CHEN D Y, ZHANG Y D, et al. TG-FTIR analysis of bio-oil and its pyrolysis/gasification property[J]. Journal of Fuel Chemistry and Technology, 2012, (10):1194-1199.
[9]	PANIGRAHI S, CHAUDHARI S T, BAKHSHI N N, et al. Production of synthesis gas/high-Btu gaseous fuel from pyrolysis of biomass-derived oil[J]. Energy & Fuels, 2002, 16(6):1392-1397.
[10]	张鹏. 生物油模型物催化气化制备氢气的研究[D]. 合肥:安徽理工大学, 2012. ZHANG P. Hydrogen preparation from catalytic gasification of bio-oil model compound[D]. Hefei:Anhui University of Science and Technology, 2012.
[11]	吴层, 颜涌捷, 张素平, 等. 生物质快速裂解油水蒸气催化重整制氢的研究[J]. 太阳能学报, 2008, 29(9):1144-1148. WU C, YAN Y J, ZHANG S P, et al. Study on hydrogen production via catalytic steam reforming of fast pyrolysis bio-oil[J]. Acta Energiae Solaris Sinica, 2008, 29(9):1144-1148.
[12]	ZHENG J L, ZHU M Q, WEN J L, et al. Gasification of bio-oil:effects of equivalence ratio and gasifying agents on product distribution and gasification efficiency[J]. Bioresource Technology, 2016, 211:164-172.
[13]	MEDRANO J A, OLIVA M, RUIZ J, et al. Hydrogen from aqueous fraction of biomass pyrolysis liquids by catalytic steam reforming in fluidized bed[J]. Energy, 2011, 36(4):2215-2224.
[14]	DAVIDIAN T, GUILHAUME N, IOJOIU E, et al. Hydrogen production from crude pyrolysis oil by a sequential catalytic process[J]. Applied Catalysis B:Environmental, 2007, 73(1):116-127.
[15]	YUNG M M, JABLONSKI W S, MAGRINI-BAIR K A. Review of catalytic conditioning of biomass-derived syngas[J]. Energy & Fuels, 2009, 23(4):1874-1887.
[16]	李顺清, 雷廷宙, 朱金陵, 等. Ru-Cu-Ni-CeO2/HZSM-5催化剂裂解秸秆气化焦油性能研究[J]. 河南科学, 2012, 30(9):1251-1255. LI S Q, LEI T J, ZHU J L, et al. Cracking of tar from straw gasification over Ru-Cu-Ni-CeO2/HZSM-5 catalysts[J]. Henan Science, 2012, 30(9):1251-1255.
[17]	WU C, HUANG Q, SUI M, et al. Hydrogen production via catalytic steam reforming of fast pyrolysis bio-oil in a two-stage fixed bed reactor system[J]. Fuel Processing Technology, 2008, 89(12):1306-1316.
[18]	贾立. 生物质热解气白云石催化重整的实验研究[D]. 武汉:华中科技大学, 2007. JIA L. An experimental research on reforming pyrolyzation gas with dolomite[D]. Wuhan:Huazhong University of Science and Technology, 2007.
[19]	周丛丛. 生物质焦油水蒸气重整橄榄石载铁催化剂的研究[D]. 大连:大连理工大学, 2013. ZHOU C C. Effect of Fe2O3/olivine on the catalytic steam reforming of bio-oil[D]. Dalian:Dalian University of Technology, 2013.
[20]	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.
[21]	吕俊复, 岳光溪. 氧化钙条件下焦油主要组分的催化裂解[J]. 清华大学学报(自然科学版), 1997, 37(2):6-10. LÜ J F, YUE G X. Catalytic cracking reactions of tar components over CaO[J]. Journal of Tsinghua University (Science and Technology), 1997, 37(2):6-10.
[22]	吴娟, 陈海军, 朱跃钊, 等. 基于回收理念的生物质燃气焦油脱除研究进展[J]. 化工进展, 2013, 32(9):2099-2105. WU J, CHEN H J, ZHU Y Z, et al. Biomass producer gas tar removal technology based on recovery idea[J]. Chemical Industry and Engineering Progress, 2013, 32(9):2099-2105.
[23]	裴闯, 张光义, 李文秀, 等. 高掺量油页岩灰制备烧结砖实验研究[J]. 新型建筑材料, 2016, (8):106-114. PEI C, ZHANG G Y, LI W X, et al. Experimental research on sintered brick preparation from oil shale ash with high blend dosage[J]. New Building Materials, 2016, (8):106-114.
[24]	MAI U, SOMELAR P, RAADO L M, et al. Oil shale ash based backfilling concrete-strength development, mineral transformations and leachability[J]. Construction & Building Materials, 2016, 102:620-630.
[25]	LAI D, CHEN Z, LIN L, et al. Secondary cracking and upgrading of shale oil from pyrolyzing oil shale over shale ash[J]. Energy & Fuels, 2015, 29(4):2219-2226.
[26]	惠世恩, 梁凌, 刘长春, 等. 升温速率、气氛与粒径对玉米秸秆热解特性的影响[J]. 热力发电, 2014, (5):59-64. HUI S E, LIANG L, LIU C C, et al. Effects of heating rate, atmosphere and particle size on corn stalk's pyrolysis characteristics[J]. Thermal Power Eneration, 2014, (5):59-64.
[27]	GARCIA-PEREZ M, WANG X S, SHEN J, et al. Fast pyrolysis of oil mallee woody biomass:effect of temperature on the yield and quality of pyrolysis products[J]. Industrial & Engineering Chemistry Research, 2008, 47(6):1846-1854.
[28]	NIU Y, TAN H, LIU Y, et al. The effect of particle size and heating rate on pyrolysis of waste capsicum stalks biomass[J]. Energy Sources, Part A:Recovery, Utilization, and Environmental Effects, 2013, 35(17):1663-1669.
[29]	江程程, 肖波, 胡智泉, 等. 不同气氛下生物质焦油气化制备合成气[J]. 安徽农业科学, 2011, 39(24):14775-14777. JIANG C C, HU B, HU Z Q, et al. Gasification of tar from biomass pyrolysis for syngas under different atmospheres[J]. Journal of Anhui Agricultural Sciences, 2011, 39(24):14775-14777.
[30]	常风民, 王启宝, 贾晋炜, 等. 城市污泥两段式催化热解制合成气研究[J]. 中国环境科学, 2015, 35(3):804-810. CHANG F M, WANG Q B, JIA J W, et al. Two-stage catalytic pyrolysis of sewage sludge for syngas production[J]. China Environmental Science, 2015, 35(3):804-810.
[31]	CHEN Y, LUO Y, WU W, et al. Experimental investigation on tar formation and destruction in a lab-scale two-stage reactor[J]. Energy & Fuels, 2009, 23(9):4659-4667.
[32]	张郑磊, 柳丹, 王晋权. 不同催化剂下玉米秸秆热解产物特性研究[J]. 锅炉技术, 2008, (6):75-78. ZHANG Z L, LIU D, WANG J Q. Research about the pyrolysis products characteristics of corn stalk with different catalysts[J]. Boiler Technology, 2008, (6):75-78.
[33]	BACKMAN R, SKRIFVARS B J, HUPA M, et al. Flue gas and dust chemistry in recovery boilers with high levels of chlorine and potassium[J]. Journal of Pulp & Paper Science, 1996, 22:J119-J126.