低含油率油页岩的热解研究
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摘要
油页岩是一种固体可燃矿产,由矿物质和有机质组成,热解(干馏)可以得到碳氢比类似天然石油的页岩油,是一种比较理想的石油替代品。我国油页岩资源丰富,保守预测储量约为4000亿吨,在我国已探明的油页岩资源中占多数的低含油率油页岩(含油率<6%)没有得到有效利用,主要原因是它在热解过程中无法实现能量的自给自足。
本文首次采用了低含油率油页岩中加入煤和废旧高分子材料的共热解的方法研究其共热解的规律。
在自制的热解装置中进行了抚顺低含油率油页岩和少量煤及少量废旧高分子材料的共热解实验,同时,还进行了相关的热重分析热解动力学分析以及油品族组成分析进行论证。实验结果表明:低含油率油页岩热解获得较高产油率的较佳反应条件是热解恒温温度520℃、热解恒温时间是20min、载气流量0.3slm;在共热解过程中油页岩和煤发生了协同作用,出现了增油减水的现象并且产油率明显增高;低含油率油页岩和废旧高分子材料共热解在产油率上未发现协同作用,但是后者为前者补充了热解能量,前者成为后者的热载体,同时也为废旧高分子材料经济的制油提供了一个有效的方法;低含油率油页岩和煤的热解进程基本接近同步,在热解动力学方面也具有相似性,具备了发生协同作用的条件;油页岩与煤共热解产生的热解油族组成变化不大,油页岩与废旧高分子材料热解的脂肪族含量明显增大改善了页岩油的品质。因此,低含油率油页岩和煤及废旧高分子材料共热解能够实现低含油率油页岩热解制油的目的。
Oil shale is a combustible solid mineral resource. It is composed of mineral and organic matter, after pyrolysis can get shale oil in which ratio of H and C is as much as crude oil, which is an ideal substitute of oil. There is abundant oil shale in China. As the conservative forecast there are 400 billion tons of reserves. Now, low oil content (below 6%) oil shale which is in the majority in our country hasn't been made good use of. The main reason is that during the pyrolysis it can not realize the self-sufficiency of heat.The rules of co-pyrolysis are studied with a new method originally----combining low oil content oil shale with coal and waste polymer material respectively.Co-pyrolysis experiment is carried out with Fushun low oil content oil shale and a few coal/waste polymer materials in a set of self-made pyrolysis equipments. The result is demonstrated that through thermo-gravimetric analysis, pyrolysis kinetics analysis and oil production composition analysis. The result shows that, through pyrolysis, the oil production of low oil content oil shale is the highest when the flux of carrier gas is 0.3slm at a constant temperature of 520℃ for 20 min; during the co-pyrolysis, synergetic effect between oil and coal occur, oil increasing, water reducing and oil production increase obviously; It is found that the synergetic effect on oil production of low oil content oil shale and waste polymer material never occur. But the latter make up the heat for the former, and the former can be the heat carrier of the latter, which provide an effective economical method for waste polymer material to make oil. The pyrolysis of low oil content oil shale and coal occur almost synchronously, which is similar on pyrolysis kinetics, so the synergetic effect can occur. The composition of oil after co-pyrolysis between oil shale and coal doesn't change much, but the acyclic content after co-pyrolysis between oil shale and waste polymer material increase obviously, improving the quality of oil shale. Therefore, co-pyrolysis of low oil content oil shale and coal/ waste polymer material can realize the purpose of making oil during pyrolysis of low oil content oil shale.
本文首次采用了低含油率油页岩中加入煤和废旧高分子材料的共热解的方法研究其共热解的规律。
在自制的热解装置中进行了抚顺低含油率油页岩和少量煤及少量废旧高分子材料的共热解实验,同时,还进行了相关的热重分析热解动力学分析以及油品族组成分析进行论证。实验结果表明:低含油率油页岩热解获得较高产油率的较佳反应条件是热解恒温温度520℃、热解恒温时间是20min、载气流量0.3slm;在共热解过程中油页岩和煤发生了协同作用,出现了增油减水的现象并且产油率明显增高;低含油率油页岩和废旧高分子材料共热解在产油率上未发现协同作用,但是后者为前者补充了热解能量,前者成为后者的热载体,同时也为废旧高分子材料经济的制油提供了一个有效的方法;低含油率油页岩和煤的热解进程基本接近同步,在热解动力学方面也具有相似性,具备了发生协同作用的条件;油页岩与煤共热解产生的热解油族组成变化不大,油页岩与废旧高分子材料热解的脂肪族含量明显增大改善了页岩油的品质。因此,低含油率油页岩和煤及废旧高分子材料共热解能够实现低含油率油页岩热解制油的目的。
Oil shale is a combustible solid mineral resource. It is composed of mineral and organic matter, after pyrolysis can get shale oil in which ratio of H and C is as much as crude oil, which is an ideal substitute of oil. There is abundant oil shale in China. As the conservative forecast there are 400 billion tons of reserves. Now, low oil content (below 6%) oil shale which is in the majority in our country hasn't been made good use of. The main reason is that during the pyrolysis it can not realize the self-sufficiency of heat.The rules of co-pyrolysis are studied with a new method originally----combining low oil content oil shale with coal and waste polymer material respectively.Co-pyrolysis experiment is carried out with Fushun low oil content oil shale and a few coal/waste polymer materials in a set of self-made pyrolysis equipments. The result is demonstrated that through thermo-gravimetric analysis, pyrolysis kinetics analysis and oil production composition analysis. The result shows that, through pyrolysis, the oil production of low oil content oil shale is the highest when the flux of carrier gas is 0.3slm at a constant temperature of 520℃ for 20 min; during the co-pyrolysis, synergetic effect between oil and coal occur, oil increasing, water reducing and oil production increase obviously; It is found that the synergetic effect on oil production of low oil content oil shale and waste polymer material never occur. But the latter make up the heat for the former, and the former can be the heat carrier of the latter, which provide an effective economical method for waste polymer material to make oil. The pyrolysis of low oil content oil shale and coal occur almost synchronously, which is similar on pyrolysis kinetics, so the synergetic effect can occur. The composition of oil after co-pyrolysis between oil shale and coal doesn't change much, but the acyclic content after co-pyrolysis between oil shale and waste polymer material increase obviously, improving the quality of oil shale. Therefore, co-pyrolysis of low oil content oil shale and coal/ waste polymer material can realize the purpose of making oil during pyrolysis of low oil content oil shale.
引文
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[2] 肇永辉.我国油页岩的主要性质及利用.沈阳化工,2000,29(1):37-39
[3] 周庆凡.世界能源及其分布状况[J].中国能源,2001,(10):27-30
[4] 何红梅,徐德平,张香兰.油页岩的开发与利用.洁净煤技术,2002,8(2):44-47
[5] 高健.世界各国油页岩干馏技术简介.煤炭加工与综合利用,2003,2:44-46
[6] Knutson C F. Developments in oil shale in 1989 [J]. AAPG,1990,74(10B):372-379
[7] Knutson C F. Developments in oil shale in 1985 [J]. AAPG, 1990, 69(10):1882-1889
[8] John R. Dyni. Origin and resources of some world oil shale deposits, Symposium on oil shale, Abstract, 2002, 11: 7
[9] J. O. Jaber, M. S. Mohsen, M. Amr. Where to with Jordanian oil shale, Oil Shale, 2001, 18(4): 315-334
[10] B. Avid, B. Purevsuren. Chemical composition of organic matter of the Mongolian Khoot oil shale, 2001,18(1):15-23
[11] L. Ballice. Classification of volatile products of temperature-programmed co-pyrolysis of Turkish Soma lignite and Goynuk oil shale, Oil Shale, 2002,19(1):57-73
[12] J. O. Jaber, S. D. Probert, O. Badr. Prospects for the exploitation of Jodanian oil shale, Oil Shale, Vol. 14, No. 4, pp. 565-578, 1997.
[13] V. Yefimov. creation of oil shale industry in Kazakhstan may become a reality, Oil Shale, 1996,13(3):247-248
[14] K. Gulec, A. ONEN. Turkish oil shale: Reserves, characterization and utilization studies, 1992 Eastern oil shale symposium, Proceedings, Kentucky, USA, 1993
[15] John R. Dyni. Oil Shale report, Oil shale reserves, D:\EMD\OS-EMD.DOC, Revised: 2/27/00, U.S. Geological Survey, USA, 2000
[16] 游君君,叶松青,刘招君等.油页岩的综合开发与利用.世界地质,23(3):261-265
[17] 钱家麟.中国页岩油工业[M].上海:华东石油学院,1983
[18] 秦宏,姜秀民,孙键等.中国油页岩的能源利用.节能,12:17-19
[19] Rein Hanni. Energy and valuble material by-product from firing Estonian oil shale[J].Waste Management, 1996,13(2):97-99
[20] 陈应泰,刘文彬.国外油页岩综合利用的进展[J].地球科学进展,1992,7(2):48-50
[21] 郭树才.油页岩干馏基础[M].大连:大连工学院煤化工研究室,1982
[22] M. P. Martignoni, D. L. Bachmann, E. F. Stoppa, W. J. B. Rodnignes. Petrosix oil shale technology learning curve, Symposium on oil shale, Abstract, Tallinn, Estonia, 2002,11: 30
[23] Joao P. Hohmann, Waldier P. Martignoni, Rubers E. M. Novicki, EdwinM. Piper; Petrosix-A successful oil shale operational complex, Eastern oil shale symposium, Proceedings, Kentucky, USA, 1992, 11: 4-11
[24] W. Taciuk. The Alberta Taciuk proces-Capacibilities for modern production of shale oil, Symposium on oil shale, Abstract, Tallinn, Estonia, 2002,11:27
[25] Y. Yefimov, S. Doilov. Efficiency of processing oil shale in 1000 ton per day retort using different arrangement of outlets for oil vapors, Oil Shale, 1999,16(4):455-463
[26] Nikolai Golubev. solid heat carrier technology for oil shale retorting, Symposium on oil shale, Abstract, Tallinn, Estonia, 2002,11:45-47
[27] J. Opik, N. Golubev, A. Kaidalov, J. Kann, A. Elenurm. Current status of oil shale processing in solid heat carrier UTT(Galoter) retorts in Eastonia, Oil Shale, 2001, 18(2):98-108
[28] Guo Shucai, Luo Changqi, Han Zhuang. Lignite retorting using solid heat carrier. Fuel Science&Technology international, 1990, 8(1):39-50
[29] 韩壮,郭树才,罗长齐,张代佳.神府煤固体热载体法快速热解的研究.煤炭转化,1992,15(3):56-62
[30] Guo Shucai, Luo Changqi, Han Zhuang. Advanced development of new technology for lignite retorting. The 4th Japan-China symposium on coal and C, chemistry proceedings 1993-05-25～28. Osaka, 123-128
[31] 郭树才.煤化学工程.北京:冶金工业出版社,1991.
[32] 马林转,何屏,王华.煤与生物质的热解.贵州化工,2004,29(1):20-23
[33] 廖洪强,孙成功,李保庆.煤一焦炉气共热解特性研究Ⅱ.煤炭转化,1997,25(3):207-212
[34] 廖洪强,孙成功,李保庆.煤一焦炉气共热解特性研究Ⅲ.煤炭转化,1998,26(1):7-12
[35] 廖洪强,孙成功,李保庆.煤一焦炉气共热解特性研究Ⅳ.煤炭转化,1998,26(1):13-17
[36] 廖洪强,孙成功,李保庆.富氢气氛下煤热解特性的研究.燃料化学学报,1998,26(2):114-118
[37] 朱学栋,朱子彬,唐黎华等.煤的热解研究.华东理工大学学报,1998,24(1):37-41
[38] 李世光,徐绍平.煤与生物质的共热解.煤炭转化,2002,25(1):7-12
[39] 聂恒锐,郭树才,赵树昌.褐煤和油页岩块快速热解研究.大连工学院学报,1982,21(4):341-347
[40] 任桂兰,杨泽志,李青山.21世纪的新资源—废旧高分子材料的回收和利用.化工时刊,2002,10.22-24
[41] Akar et al. Production of chemicals from oil shales. Elsevier Science Ltd, 1995, 8: 1113-1117
[42] 邢大立.《废旧高分子材料》课程中的废旧材料资源利用问题.东莞理工学院学报,2000,7(1):99-102
[43] J. Gersten et al. Utilization of waste polymers through one-stage low-temperature pyrolysis of oil shale. Fuel, 1999 (78),987-990
[44] J. Gersten et al. Kinetic study of the thermal decomposition of polypropylene, oil shale, and their mixture, Fuel,2000(79),1679-1686
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