内构件移动床固体热载体油页岩热解技术

doi:10.11949/j.issn.0438-1157.20171051

摘要/Abstract

摘要：

从化学反应工程角度分析了小颗粒油页岩热解技术存在的共性问题和初级热解与二次反应的关系，提出了定向调控热解产物流动及其与挥发分反应匹配的方法。针对小颗粒油页岩热解制备高收率和高品质页岩油的技术需求，创新性地提出了内构件移动床固体热载体油页岩热解技术，通过内构件调控热解挥发分在反应器内的流动，实现热解油气原位过滤除尘和选择性裂解提质，以解决现有固体热载体热解技术长期面临的所产页岩油中含尘量高、重质组分高和油收率低等问题。建立了10 kg·h^-1内构件移动床固体热载体油页岩热解模式装置，验证了新工艺的可行性和先进性，展示出良好的技术应用前景。

关键词: 油页岩, 热解, 二次反应, 内构件, 移动床, 固体热载体

Abstract:

From a chemical reaction engineering point of view,the relationship between primary pyrolysis and secondary reactions of small-size oil shale pyrolysis technologies was analyzed.A novel method was proposed to regulate pyrolysis volatiles to flow in an expected direction and to match their secondary reactions to flow/transfer fields in the reactor.A new technology of solid heat carrier pyrolysis was further developed on moving bed reactor with particularly designed internals to overcome challenges for small-size oil shale pyrolysis,including low oil yield,high contents of dust,and heavy components.In such internal-structured moving bed reactor,pyrolysis volatiles flew laterally across particle bed in order to realize in-bed dust removal via filtering and in-situ oil upgrade through ash-involved selective secondary reactions.A 10 kg·h^-1 laboratory setup built to assess the new solid heat carrier pyrolysis technology adopting internal-structured moving bed showed shale oil product at high yield and high quality from small-size oil shale.The results presented a good application prospective of the proposed pyrolysis reactor and process.

Key words: oil shale, pyrolysis, secondary reactions, internals, moving bed, solid heat carrier

中图分类号:

TQ519

赖登国, 战金辉, 陈兆辉, 韩振南, 武荣成, 许光文. 内构件移动床固体热载体油页岩热解技术[J]. 化工学报, 2017, 68(10): 3647-3657.

LAI Dengguo, ZHAN Jinhui, CHEN Zhaohui, HAN Zhennan, WU Rongcheng, XU Guangwen. Oil shale pyrolysis by solid heat carrier in internal-structured moving bed[J]. CIESC Journal, 2017, 68(10): 3647-3657.

参考文献 41

[1]	陈兆辉, 敦启孟, 石勇, 等. 热解温度和反应气氛对输送床煤快速热解的影响[J]. 化工学报, 2017, 68(4):1566-1573. CHEN Z H, DUN Q M, SHI Y, et al. Effects of pyrolysis temperature and atmosphere on rapid coal pyrolysis in transport bed reactor[J]. CIESC Journal, 2017, 68(4):1566-1573.
[2]	贾承造, 郑民, 张永峰. 中国非常规油气资源与勘探开发前景[J]. 石油勘探与开发, 2012, 39(2):129-136. JIA C Z, ZHENG M, ZHANG Y F. Unconventional hydrocarbon resources in China and the prospect of exploration and development[J]. Petroleum Exploration and Development, 2012, 39(2):129-136.
[3]	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 Sciences, 2010, 12(5):25-29.
[4]	钱家麟, 王剑秋, 李术元. 世界油页岩资源利用和发展趋势[J]. 吉林大学学报(地球科学版), 2006, 36(6):877-887. QIAN J L, WANG J Q, LI S Y. World oil shale utilization and its future[J]. Journal of Jilin University(Earth Science Edition), 2006, 36(6):877-887.
[5]	刘招君, 董清水, 叶松青, 等. 中国油页岩资源现状[J]. 吉林大学学报(地球科学版), 2006, 36(6):869-876. LIU Z J, DONG Q S, YE S Q, et al. The situation of oil shale resources in China[J]. Journal of Jilin University(Earth Science Edition), 2006, 36(6):869-876.
[6]	钱家麟, 尹亮. 油页岩:石油的补充能源[M]. 北京:中国石化出版社, 2008. QIAN J L, YIN L. Oil Shale:Oil Supplement Energy[M]. Beijing:China Petrochemical Press, 2008.
[7]	杨庆春, 周怀荣, 杨思宇, 等. 油页岩开发利用技术及系统集成的研究进展[J]. 化工学报, 2016, 67(1):109-118. YANG Q C, ZHOU H R, YANG S Y, et al. Research progress on utilization and systemic integration technologies of oil shale[J]. CIESC Journal, 2016, 67(1):109-118.
[8]	LI X X, ZHOU H R, WANG Y J, et al. Thermoeconomic analysis of oil shale retorting processes with gas or solid heat carrier[J]. Energy, 2015, 87:605-614.
[9]	曾帅, 周怀荣, 钱宇. 煤热解制油和油页岩制油技术评述与比较分析[J]. 化工学报, 2017, 68(10):3658-3668. ZENG S, ZHOU H R, QIAN Y. Review and techno-economic analysis of coal pyrolysis to liquid and oil shale to liquid processes[J]. CIESC Journal, 2017, 68(10):3658-3668.
[10]	张秋民, 关珺, 何德民. 几种典型的油页岩干馏技术[J]. 吉林大学学报(地球科学版), 2006, 36(6):1019-1026. ZHANG Q M, GUAN J, HE D M. Typical technologies for oil shale retorting[J]. Journal of Jilin University(Earth Science Edition), 2006, 36(6):1019-1026.
[11]	侯吉礼, 马跃, 李术元, 等. 世界油页岩资源的开发利用现状[J]. 化工进展, 2015, 34(5):1183-1190. HOU J L, MA Y, LI S Y, et al. Development and utilization of oil shale worldwide[J]. Chemical Industry and Engineering Process, 2015, 34(5):1183-1190.
[12]	COOK E W. Oil-shale technology in USA[J]. Fuel, 1974, 53(3):146-151.
[13]	赖登国. 内构件移动床固体热载体油页岩热解技术研究[D]. 北京:中国科学院大学, 2017. LAI D G. Pyrolysis of oil shale by solid heat carrier in moving bed with internals[D]. Beijing:University of Chinese Academy of Sciences, 2017.
[14]	李文英, 邓靖, 喻长连. 褐煤固体热载体热解提质工艺进展[J]. 煤化工, 2012, 1:1-5. LI W Y, DENG J, YU C L. Development of lignite pyrolysis with solid heat carrier[J]. Coal Chemical Industry, 2012, 1:1-5.
[15]	李文英, 喻长连, 李晓红, 等. 褐煤固体热载体催化热解研究进展[J]. 煤炭科学技术, 2012, 40(5):111-115. LI W Y, YU C L, LI X H, et al. Research progress on catalysis pyrolysis of lignite solid heat carrier[J]. Coal Science and Technology, 2012, 40(5):111-115.
[16]	秦宏, 岳耀奎, 刘洪鹏, 等. 中国油页岩干馏技术现状与发展趋势[J]. 化工进展, 2015, 34(5):1191-1198. QIN H, YUE Y K, LIU H P, et al. Current status and prospect of oil shale retorting technologies in China[J]. Chemical Industry and Engineering Process, 2015, 34(5):1191-1198.
[17]	WANG S, JIANG X M, HAN X X, et al. Investigation of Chinese oil shale resources comprehensive utilization performance[J]. Energy, 2012, 42(1):224-232.
[18]	JIANG X M, HAN X X, CUI Z G. New technology for the comprehensive utilization of Chinese oil shale resources[J]. Energy, 2007, 32(5):772-777.
[19]	刘振宇. 煤快速热解制油技术问题的化学反应工程根源:逆向传热与传质[J]. 化工学报, 2016, 67(1):1-5. LIU Z Y. Origin of common problems in fast coal pyrolysis technologies for tar:the countercurrent flow of heat and volatiles[J]. CIESC Journal, 2016, 67(1):1-5
[20]	MIURA K. Mild conversion of coal for producing valuable chemicals[J]. Fuel Processing Technology, 2000, 62(2):119-135.
[21]	畅志兵, 初茉, 张超, 等. 桦甸油页岩热解过程中热沥青的组成变化规律[J]. 燃料化学学报, 2016, 44(11):1310-1317. CHANG Z B, CHU M, ZHANG C, et al. Variation of chemical composition of thermal bitumen during Huadian oil shale pyrolysis[J]. Journal of Fuel Chemistry and Technology, 2016, 44(11):1310-1317.
[22]	BRAUN R L, ROTHMAN A J. Oil-shale pyrolysis-kinetics and mechanism of oil production[J]. Fuel, 1975, 54(2):129-131.
[23]	LI S Y, YUE C T. Study of different kinetic models for oil shale pyrolysis[J]. Fuel Processing Technology, 2004, 85(1):51-61.
[24]	BURNHAM A K, HAPPE J A. On the mechanism of kerogen pyrolysis[J]. Fuel, 1984, 63(10):1353-1356.
[25]	LAI D G, CHEN Z H, LIN L X, 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]	LAI D G, ZHAN J H, TIAN Y, et al. Mechanism of kerogen pyrolysis in terms of chemical structure transformation[J]. Fuel, 2017, 199:504-511.
[27]	张盛诚, 何榕. 单颗粒煤粉热解时焦油的二次反应和扩散[J]. 清华大学学报(自然科学版), 2016, 56(6):605-610. ZHANG S C, HE R. Secondary reactions and diffusion of tar during single coal particle pyrolysis[J]. Journal of Tsinghua University (Science and Technology), 2016, 56(6):605-610.
[28]	LIN L X, LAI D G, SHI Z, et al. Distinctive oil shale pyrolysis behavior in indirectly heated fixed bed with internals[J]. RSC Advances, 2017, 7:21467-21474.
[29]	ZHANG Y, HAN Z N, WU H, et al. Interactive matching between the temperature profile and secondary reactions of oil shale pyrolysis[J]. Energy & Fuels, 2016, 30(4):2865-2873.
[30]	LIN L X, ZHANG C, LI H J, et al. Pyrolysis in indirectly heated fixed bed with internals:the first application to oil shale[J]. Fuel Processing Technology, 2015, 138:147-155.
[31]	许光文, 高士秋, 余剑, 等. 燃料解耦热化学转化基础与技术[M]. 北京:科学出版社, 2016. XU G W, GAO S Q, YU J, et al. Thermochemical Conversion Fundamentals and Technologies Based on Decoupling for Fuels[M]. Beijing:Science Press, 2016.
[32]	战金辉, 赖登国, 许光文. 油页岩:固体石油[J]. 科学世界, 2016, 12:68-73. ZHAN J H, LAI D G, XU G W. Oil shale:solid petroleum[J]. Science World, 2016, 12:68-73.
[33]	LAI D G, CHEN Z H, SHI Y, et al. Pyrolysis of oil shale by solid heat carrier in an innovative moving bed with internals[J]. Fuel, 2015, 159:943-951.
[34]	LAI D G, ZHANG G Y, XU G W. Characterization of oil shale pyrolysis by solid heat carrier in moving bed with internals[J]. Fuel Processing Technology, 2017, 158:191-198.
[35]	LAI D G, SHI Y, GENG S L, et al. Secondary reactions in oil shale pyrolysis by solid heat carrier in a moving bed with internals[J]. Fuel, 2016, 173:138-145.
[36]	张纯. 外热式内构件移动床低阶碎煤热解技术研究[D]. 北京:中国科学院过程工程研究所, 2015. ZHANG C. Pyrolysis of small-size low-rank coal in indirectly heated moving bed with internals[D]. Beijing:Institute of Process Engineering, Chinese Academy of Sciences, 2015.
[37]	王擎, 崔达, 迟铭书, 等. 利用GC-MS与NMR技术研究干馏终温对桦甸页岩油组成性质的影响[J]. 化工学报, 2015, 66(7):2670-2677. WANG Q, CUI D, CHI M S, et al. Influence of final retorting temperature on composition and property of Huadian shale oil[J]. CIESC Journal, 2015, 66(7):2670-2677.
[38]	NAZZAL J M. The influence of grain size on the products yield and shale oil composition from the pyrolysis of Sultani oil shale[J]. Energy Conversion and Management, 2008, 49(11):3278-3286.
[39]	WILLIAMS P T, NAZZAL J M. Pyrolysis of oil shales:influence of particle grain size on polycyclic aromatic compounds in the derived shale oils[J]. Journal of the Institute of Energy, 1999, 72(491):48-55.
[40]	ZHANG C, WU R C, HU E F, et al. Coal pyrolysis for high-quality tar and gas in 100 kg fixed bed enhanced with internals[J]. Energy & Fuels, 2014, 28(11):7294-7302.
[41]	ZHANG C, WU R C, XU G W. Coal pyrolysis for high-quality tar in a fixed-bed pyrolyzer enhanced with internals[J]. Energy & Fuels, 2014, 28(1):236-244.