干馏条件对油页岩半焦孔隙结构的影响

doi:10.11949/j.issn.0438-1157.20170512

摘要/Abstract

摘要：

油页岩干馏过程中发生挥发分物质的析出，导致颗粒的孔隙结构发生重大的变化，进而会对油页岩半焦的燃烧反应、成灰等特性产生重要的影响。利用扫描电镜、氮气吸附/脱附法对不同干馏温度、不同干馏时间下制备得到的桦甸油页岩半焦进行了孔隙分析，并与前人针对相同样品的油页岩半焦燃烧特性实验研究进行了对照分析。结果表明，在实验范围内，随干馏温度增加，受热解二次反应产生的焦炭对孔隙堵塞的影响，油页岩半焦孔隙比表面积和比容积先增加后减小；随干馏时间增加，伴随着小孔之间的合并，油页岩半焦孔隙比表面积先增加后减小，比容积单调增加。

关键词: 燃料, 多孔介质, 热解, 油页岩半焦, 燃烧, 孔隙结构

Abstract:

The devolatilization of oil shale during retort process would cause significant changes to the pore structure of oil shale semi coke,which would have important effects on the semi coke combustion and ash formation.The pore structures of oil shale semi coke prepared at different retorting temperatures and different residue times were analyzed by SEM and nitrogen adsorption and desorption.The results were discussed with the combustion results of the same samples which conducted by other researchers.The results show that,the pore specific area and volume of oil shale semi coke would initially increase and then decrease with the increase of retorting temperature within experimental parameters range,which might be explained by coke blocking pore.With the increase of residue time,pore coalescence would happen.So the pore specific area of oil shale semi coke would initially increase and then decrease,while the pore specific volume would increase.

Key words: fuel, porous media, pyrolysis, oil shale semi coke, combustion, pore structure

中图分类号:

TQ028.8

黄逸群, 张缦, 单露, 杨海瑞, 岳光溪. 干馏条件对油页岩半焦孔隙结构的影响[J]. 化工学报, 2017, 68(10): 3870-3876.

HUANG Yiqun, ZHANG Man, SHAN Lu, YANG Hairui, YUE Guangxi. Effects of retorting conditions on pore structure of oil shale semi coke[J]. CIESC Journal, 2017, 68(10): 3870-3876.

参考文献 30

[1]	胡文瑞, 翟光明, 李景明. 中国非常规油气的潜力和发展[J]. 中国工程科学, 2010, 12(5):25-29. HU W R, ZHAI G M, LI J M. Potential and development of unconventional hydrocarbon resources in China[J]. Engineering Science, 2010, 12(5):25-29.
[2]	王擎, 黄宗越, 迟铭书, 等. 油页岩干酪根化学结构特性分析[J]. 化工学报, 2015, 66(5):1861-1866. WANG Q, HUANG Z Y, CHI M S, et al. Chemical structure analysis of oil shale kerogen[J]. CIESC Journal, 2015, 66(5):1861-1866.
[3]	韩向新, 姜秀民, 崔志刚, 等. 油页岩半焦热解特性[J]. 化工学报, 2006, 57(1):126-130. HAN X X, JIANG X M, CUI Z G, et al. Pyrolysis behavior of oil shale semi-coke[J]. Journal of Chemical Industry and Engineering (China), 2006, 57(1):126-130.
[4]	AL-QODAH Z, LAFI W. Adsorption of reactive dyes using shale oil ash in fixed beds[J]. Aqua, 2003, 52(3):189-198.
[5]	JIANG X M, HAN X X, CUI Z G. Progress and recent utilization trends in combustion of Chinese oil shale[J]. Progress in Energy & Combustion Science, 2007, 33(6):552-579.
[6]	王贤清, 王剑秋, 钱家麟, 等. 油页岩半焦燃烧中灰分层的扩散动力学研究[J]. 石油学报(石油加工), 1987, (4):4-11. WANG X Q, WANG J Q, QIAN J L, et al. Diffusional effects in the ash layer of the oil shale char combustion[J]. Acta Petrolei Sinica(Petroleum Processing Section), 1987, (4):4-11.
[7]	王剑秋, 王贤清. 颗粒页岩半焦燃烧反应模型的研究[J]. 石油学报(石油加工), 1987, (3):4-12. WANG J Q, WANG X Q. A study on the combustion reaction model of oil shale particles[J]. Acta Petrolei Sinica(Petroleum Processing Section), 1987, (3):4-12.
[8]	YU J, LUCAS J A, WALL T F. Formation of the structure of chars during devolatilization of pulverized coal and its thermoproperties:a review[J]. Progress in Energy & Combustion Science, 2007, 33(2):135-170.
[9]	韩向新, 姜秀民, 崔志刚, 等. 油页岩颗粒孔隙结构在燃烧过程中的变化[J]. 中国电机工程学报, 2007, 27(2):26-30. HAN X X, JIANG X M, CUI Z G, et al. Evolution of pore structure of oil shale particles during combustion[J]. Proceedings of the Chinese Society for Electrical Engineering, 2007, 27(2):26-30.
[10]	上官禾林, 冯增朝, 赵静, 等. 不同温度下油页岩的孔隙结构变化特征研究[J]. 矿业研究与开发, 2015, (3):20-22. SHANGGUAN H L, FENG Z C, ZHAO J, et al. The variation characteristics research on pore structure of oil shale under different temperature[J]. Mining Research and Development, 2015, (3):20-22.
[11]	HAN X, KULAOTS I, JIANG X, et al. Review of oil shale semicoke and its combustion utilization[J]. Fuel, 2014, 126(12):143-161.
[12]	SIMONS G A, SIMONS G A. The role of pore structure in coal pyrolysis and gasification[J]. Progress in Energy & Combustion Science, 1983, 9(4):269-290.
[13]	CHEN Q, HE R, XU X, et al. Experimental study on pore structure and apparent kinetic parameters of char combustion in kinetics-controlled regime[J]. Energy & Fuels, 2004, 18(5):1562-1568.
[14]	WANG Q, KONG L W, BAI J R, et al. The pyrolysis characteristics and pore structure of oil shale of different densities[J]. Energy Procedia, 2012, 17(Part A):876-883.
[15]	SCHRODT J T, OCAMPO A. Variations in the pore structure of oil shales during retorting and combustion[J]. Fuel, 1984, 63(11):1523-1527.
[16]	孙佰仲, 王擎, 李少华, 等. 桦甸油页岩及半焦孔结构的特性分析[J]. 动力工程学报, 2008, 28(1):163-167. SUN B Z, WANG Q, LI S H, et al. Analysis of specific area and porous structure of oil shale and semi-coke[J]. Journal of Power Engineering, 2008, 28(1):163-167.
[17]	BAI J, WANG Q, JIAO G. Study on the pore structure of oil shale during low-temperature pyrolysis[J]. Energy Procedia, 2012, 17(1):1689-1696.
[18]	HAN X, JIANG X, YAN J, et al. Effects of retorting factors on combustion properties of shale char(2):Pore structure[J]. Energy & Fuels, 2011, 25(1):97-102.
[19]	韩向新, 姜秀民, 崔志刚, 等. 干馏温度对油页岩半焦着火的影响[J]. 化学工程, 2007, 35(7):63-66. HAN X X, JIANG X M, CUI Z G, et al. Effect of carbonization temperature on ignition of oil shale semicoke[J]. Chemical Engineering, 2007, 35(7):63-66.
[20]	孙保民, 孙佰仲, 王擎, 等. 油页岩和半焦着火特性实验研究[J]. 中国电机工程学报, 2008, 28(26):59-64. SUN B M, SUN B Z, WANG Q, et al. Experiment study on ignition characteristics of oil shale and semi-coke[J]. Proceedings of the Chinese Society for Electrical Engineering, 2008, 28(26):59-64.
[21]	王擎, 孙佰仲, 吴吓华, 等. 油页岩半焦燃烧反应活性分析[J]. 化学工程, 2006, 34(11):16-19. WANG Q, SUN B Z, WU X H, et al. Analysis of combustion reaction activation of oil shale semi-coke[J]. Chemical Engineering, 2006, 34(11):16-19.
[22]	孙凯. 桦甸油页岩半焦燃烧特性研究[J]. 东北电力大学学报, 2010, 30(2):10-13. SUN K. Study on the combustion characteristics of the Huadian oil shale semi-coke[J]. Journal of Northeast Dianli University(Natural Science Edition), 2010, 30(2):10-13.
[23]	黄富, 李术元, 徐明, 等. 桦甸油页岩半焦燃烧特性及动力学研究[J]. 石油化工高等学校学报, 2011, 24(3):55-59. HUANG F, LI S Y, XU M, et al. Combustion characteristics of the semi-coke from Huadian oil shale[J]. Journal of Petrochemical Universities, 2011, 24(3):55-59.
[24]	韩向新, 姜秀民, 崔志刚, 等. 油页岩半焦燃烧特性的研究[J]. 中国电机工程学报, 2005, 25(15):106-110. HAN X X, JIANG X M, CUI Z G, et al. Study of combustion performance of oil shale semi-coke[J]. Proceedings of the Chinese Society for Electrical Engineering, 2005, 25(15):106-110.
[25]	王擎, 吴吓华, 孙佰仲, 等. 桦甸油页岩半焦燃烧反应动力学研究[J]. 中国电机工程学报, 2006, 26(7):29-34. WANG Q, WU X H, SUN B Z, et al. Combustion reaction kinetics study of Huadian oil shale semi-coke[J]. Proceedings of the Chinese Society for Electrical Engineering, 2006, 26(7):29-34.
[26]	WANG Q, WANG H, SUN B, et al. Interactions between oil shale and its semi-coke during co-combustion[J]. Fuel, 2009, 88(8):1520-1529.
[27]	李晓栋, 樊保国, 金燕, 等. 油页岩半焦燃烧特性试验研究[J]. 煤炭学报, 2016, 41(10):2473-2478. LI X D, FAN B G, JIN Y, et al. Experimental study on combustion characteristics of oil shale semi-coke[J]. Journal of China Coal Society, 2016, 41(10):2473-2478.
[28]	严继民. 吸附与凝聚[M]. 北京:科学出版社, 1986. YAN J M. Adsorption and Condensation[M]. Beijing:Science Press, 1986.
[29]	WILLIAMS P T, AHMAD N. Influence of process conditions on the pyrolysis of Pakistani oil shales[J]. Fuel, 1999, 78(6):653-662.
[30]	GERASIMOV G, VOLKOV E. Modeling study of oil shale pyrolysis in rotary drum reactor by solid heat carrier[J]. Fuel Processing Technology, 2015, 139:108-116.