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摘要: 以遵义无烟煤煤焦为气化原料，以稻草灰和棉秆灰为生物质灰添加剂，基于热重分析仪开展焦样-CO2等温气化实验，以探究生物质灰添加对煤焦气化反应特性的影响，并基于气化过程焦样固体结构演变对其进行关联解释。研究表明，稻草灰和棉杆灰的添加有利于提高煤焦气化反应活性，这主要归因于生物质灰添加有利于气化过程煤焦活性矿物质含量增加和碳结构有序度降低。且稻草灰和棉秆灰的添加对焦样气化反应活性的增加幅度随气化温度升高而减小，这可解释为生物质灰添加对气化过程煤焦活性矿物质含量增加和碳结构有序度降低的幅度随气化温度升高而减小。此外，棉秆灰对煤焦气化反应活性的促进作用较稻草灰更为显著，这主要由于棉杆灰的添加对气化半焦中活性AAEM含量的增加作用以及碳结构石墨化进程的抑制作用更加明显。Abstract: Zunyi anthracite was used as the raw material of gasification and rice straw ash and cotton stalk ash were optioned as biomass ash additives. Char-CO2 isothermal gasification experiments were conducted using TGA to investigate the effect of biomass ash addition on coal char gasification characteristics. Furthermore, the relationship between char structure evolution during gasification and char gasification reactivity was investigated. The results indicate that the biomass ash addition has a promotion effect on coal char gasification, which is well related to the increase in active AAEM content and the decrease in the order degree of carbon structure of chars by the addition of biomass ash. However, the promotion effect of biomass ash additives on coal char gasification is weakened with increasing gasification temperature, mainly due to that the positive effect of biomass ash additive on the increase of active AAEM content in char and the inhibition effect of biomass ash additive on carbon structure order degree of coal char become weaker at higher gasification temperature. Additionally, it is found that cotton stalk ash has a more significant positive effect on coal char gasification than rice straw ash because cotton stalk ash has a more obvious effect on the increase in active AAEM content and the decrease in the carbon structure graphitization degree of coal char.
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Key words:
- biomass ash /
- coal char /
- gasification characteristic /
- structure evolution
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图 2 焦样碳转化率随气化时间的变化
Figure 2 Curves of carbon conversion of coal char samples versus gasification time
图 3 添加生物质灰焦样相对反应活性指数
Figure 3 Relative reactivity index curves of coal char samples with biomass ash additive
图 4 遵义热解焦气化半焦的拉曼光谱拟合曲线
Figure 4 Fitting curve of Raman spectrum of ZY-800P gasified semi-char
表 1 煤样的工业分析和元素分析
Table 1 Proximate and ultimate analyses of ZY sample
Sample Proximate analysis wd /% Ultimate analysis wd /% V FC A C H N O S ZY 7.59 73.46 18.95 76.57 2.13 1.10 0.83 0.42 
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表 2 煤灰和生物质灰化学组成
Table 2 Ash chemical composition of tested samples
Sample Ash composition /% SiO2 Al2O3 K2O Na2O CaO Fe2O3 MgO ZY 55.67 30.63 1.04 1.64 0.95 4.45 0.59 RS 58.88 0.18 21.97 1.13 4.20 0.26 2.73 CS 1.73 0.35 40.96 6.99 20.60 0.51 9.38
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表 3 焦样气化反应活性指数
Table 3 Gasification reactivity index of coal char samples
Temperature t/℃ R0.9 ZY-800P ZY-800P-RSA ZY-800P-CSA 850 - 0.001 0.009 900 0.001 0.002 0.017 950 0.003 0.005 0.031 1000 0.007 0.009 0.057
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表 4 气化半焦中活性AAEM含量
Table 4 Active AAEM contents in gasified semi-char of individual and blended chars
Sample Active AAEM content/(mg·g-1 semi-char) K Na Ca total ZY-800P-900G ~0 0.45 4.15 4.60 ZY-800P-1000G ~0 0.40 3.71 4.11 ZY-800P-RSA-900G 0.43 0.79 4.06 5.28 ZY-800P-RSA-1000G 0.24 0.57 3.61 4.42 ZY-800P-CSA-900G 3.94 1.07 8.40 13.41 ZY-800P-CSA-1000G 1.88 1.01 7.38 10.27
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表 5 气化半焦拉曼光谱峰面积比
Table 5 Raman band area ratio of gasification semi-chars
Gasification temp. t/℃ ID1/IG ZY-800P ZY-800P-RSA ZY-800P-CSA 900 4.85 4.93 5.16 1000 4.62 4.66 4.78
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[1] 杨景标, 蔡宁生, 张彦文.催化剂添加量对褐煤焦水蒸气气化反应性的影响[J].燃料化学学报, 2008, 36(1):15-21. doi: 10.3969/j.issn.0253-2409.2008.01.004YANG Jing-biao, CAI Ning-sheng, ZHANG Yan-wen. Effect of catalyst loadings on the gasification reactivity of a lignite char with steam[J]. J Fuel Chem Technol, 2008, 36(1):15-21. doi: 10.3969/j.issn.0253-2409.2008.01.004 [2] 李少华, 王艳鹏, 车德勇, 刘大任, 张卓文.松木屑与褐煤催化共气化特性实验研究[J].热力发电, 2015, 44(1):44-48. doi: 10.3969/j.issn.1002-3364.2015.01.044LI Shao-hua, WANG Yan-peng, CHE De-yong, LIU Da-ren, ZHANG Zhuo-wen. Experimental study on catalytic co-gasification characteristics of pine sawdust and lignite[J]. Therm Power Gener, 2015, 44(1):44-48. doi: 10.3969/j.issn.1002-3364.2015.01.044 [3] 连明磊, 谢军, 武文芳, 葛源, 霍霞, 白志玲.微波辅助气流床煤气化工艺研究[J].煤炭科学技术, 2018, 46(3):218-223. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=MTKJ201803036&dbname=CJFD&dbcode=CJFQLIAN Ming-lei, XIE Jun, WU Wen-fang, GE Yuan, HUO Xia, BAI Zhi-ling. Process study on microwave-assisted entrained flow gasification[J]. Coal Sci Technol, 2018, 46(3):218-223. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=MTKJ201803036&dbname=CJFD&dbcode=CJFQ [4] RIZKIANA J, GUAN G Q, WIDAYATNO W B, HAO X G, LI X M, HUANG W, ABDULA A. Promoting effect of vrious biomass ashes on the steam gasification of low-rank coal[J]. Appl Energy, 2014, 133:282-288. doi: 10.1016/j.apenergy.2014.07.091 [5] ASSILEV S V, BAXTER D, ANDERSEN L K, VASSLIEVA C G. An overview of the composition and application of biomass ash[J]. Fuel, 2013, 105:19-39. doi: 10.1016/j.fuel.2012.10.001 [6] 朱志辉, 李冰浪.恒温下生物质灰对煤焦气化特性的影响[J].电力科学与工程, 2017, 33(8):67-71. doi: 10.3969/j.ISSN.1672-0792.2017.08.011ZHU Zhi-hui, LI Bin-lang. Effect of biomass ash on char gasification under constant temperature[J]. Electr Power Sci Eng, 2017, 33(8):67-71. doi: 10.3969/j.ISSN.1672-0792.2017.08.011 [7] 郭辰辰, 董卫果.煤的碱金属催化气化研究新进展[J].煤质技术, 2016, 3:38-42. http://d.old.wanfangdata.com.cn/Periodical/mzjs201603013GUO Chen-chen, DONG Wei-guo. New research prograss on the alkali metal catalytic gasification of coal[J]. Coal Qual Technol, 2016, 3:38-42. http://d.old.wanfangdata.com.cn/Periodical/mzjs201603013 [8] NANOU P, MURILLO H G, SWAAIJ W, ROSSUM G V, KERSTEN R A. Intrinsic reactivity of biomass-derived char under steam gasification conditions-potential of wood ash as catalyst[J]. Chem Eng J, 2013, 217:289-299. doi: 10.1016/j.cej.2012.12.012 [9] 齐晓宾, 宋国良, 宋维健, 吕清刚.准东高碱煤气化过程中碱金属迁移与结渣特性实验研究[J].燃料化学学报, 2015, 43(8):906-913. doi: 10.3969/j.issn.0253-2409.2015.08.002QI Xiao-bin, SONG Guo-liang, SONG Wei-jian, LÜ Qing-gang. Alkali metal migration and slagging characteristic during Zhundong high-alkali coal gasification[J]. J Fuel Chem Technol, 2015, 43(8):906-913. doi: 10.3969/j.issn.0253-2409.2015.08.002 [10] TIBERIU P, FAN M H, MORRIS D, SLIMANE R B, BELL D A, TOWLER B F. Catalytic gasification of a powder river basin coal[J]. Fuel, 2013, 103:161-170. doi: 10.1016/j.fuel.2012.08.049 [11] HUANG S, WU S, WU Y, GAO J. The physicochemical properties and catalytic characteristics of different biomass ashes[J]. Energy Source Part A, 2014, 36:402-410. doi: 10.1080/15567036.2012.722746 [12] ZHANG Z Y, PANG S S, LEVI T. Influence of AAEM species in coal and biomass on steam co-gasification of chars of blended coal and biomass[J]. Renew Energy, 2017, 101:356-363. doi: 10.1016/j.renene.2016.08.070 [13] HUO W, ZHOU Z J, WANG F C, YU G S. Mechanism analysis and experimental verification of pore diffusion on coke and coal char gasification with CO2[J]. Chem Eng J, 2014, 244:227-233. doi: 10.1016/j.cej.2014.01.069 [14] POPA T, FAN M, ARGYLE M D, SLIMANE R B, BELL D A, TOWLER B F. Catalytic gasification of a powder river basin coal[J]. Fuel Process Technol, 2013, 103:161-170. http://cn.bing.com/academic/profile?id=6f55d71aa9729abde0d7772a91dd61d3&encoded=0&v=paper_preview&mkt=zh-cn [15] 刘洋, 杨新芳, 雷福林, 肖云汉.添加CaO的准东煤中温水蒸气气化特性的研究[J].燃料化学学报, 2018, 46(3):265-272. doi: 10.3969/j.issn.0253-2409.2018.03.002LIU Yang, YANG Xin-fang, LEI Fu-lin, XIAO Yun-han. Steam gasification characteristics of Zhundong coal with additive CaO at medium temperature[J]. J Fuel Chem Technol, 2018, 46(3):265-272. doi: 10.3969/j.issn.0253-2409.2018.03.002 [16] WEI J T, GUO Q H, HE Q, DING L, YOSHIKAWA K, YU G S. Co-gasification of bituminous coal and hydrochar derived from municipal solid waste:Reactivity and synergy[J]. Bioresour Technol, 2017, 239:482-489. doi: 10.1016/j.biortech.2017.05.014 [17] MITSUOKA K, HAYASHI S, AMANO H, KAYAHARA K, SASAOAKA E, UDDIN M A. Gasification of woody biomass char with CO2:The catalytic effects of K and Ca species on char gasification reactivity[J]. Fuel Process Technol, 2011, 92:26-31. doi: 10.1016/j.fuproc.2010.08.015 [18] LI Y, YANG H, HU J, WANG X, CHEN H. Effect of catalysts on the reactivity and structure evolution of char in petroleum coke steam gasification[J]. Fuel, 2014, 117:1174-1180. doi: 10.1016/j.fuel.2013.08.066 [19] TAY H L, KAJITANI S, WANG S, LI C. A preliminary Raman spectroscopic perspective for the roles of catalysts during char gasification[J]. Fuel, 2014, 121:165-172. doi: 10.1016/j.fuel.2013.12.030 [20] ZHU H L, YU G S, GUO Q H, WANG X J. In situ Raman Spectroscopy study on catalytic pyrolysis of a bituminous coal[J]. Energy Fuels, 2017, 31:5817-5827. doi: 10.1021/acs.energyfuels.6b03042 [21] SOLOMON P R, CARANGELO R M. FTIR analysis of coal. 1. Techniques and determination of hydroxyl concentrations[J]. Fuel, 1982, 61(7):663-669. doi: 10.1016/0016-2361(82)90014-X -
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