欢迎访问过程工程学报, 今天是
过程与工艺

温度和停留时间对煤热解挥发分二次反应的影响

  • 敦启孟 陈兆辉 皇甫林 周杨 余剑 高士秋 刘鸿雁
展开
  • 1. 河北工业大学化工学院,天津 300130;2. 中国科学院过程工程研究所多相复杂系统国家重点实验室,北京 100190

收稿日期: 2017-03-24

  修回日期: 2017-05-11

  网络出版日期: 2018-01-29

基金资助

国家重点研发计划资助项目

Influences of Temperature and Residence Time on Secondary Reactions of Volatiles from Coal Pyrolysis

  • Qimeng DUN Zhaohui CHEN Fulin HUANG Yang ZHOU Jian YU Shiqiu GAO Hongyan LIU
Expand
  • 1. School of Chemical Engineering, Hebei University of Technology, Tianjin 300130, China; 2. State Key Laboratory of Multi-phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

Received date: 2017-03-24

  Revised date: 2017-05-11

  Online published: 2018-01-29

摘要

在两段固定床反应器中考察了温度和停留时间对煤热解挥发分二次反应产物分布的影响. 结果表明,温度和停留时间对二次反应的影响相互关联. 温度≤600℃、停留时间小于2 s时,挥发分基本不发生气相二次反应. 随温度升高和停留时间延长,挥发分二次反应加剧,焦油产率下降,气体产率和积碳产率增加. 温度低于700℃时,焦油主要转化为气体产物,气相二次反应由二次裂解反应控制;高于700℃时,焦油转化为气体和积碳,气相二次反应由裂解反应和结焦反应共同控制. 提高二次反应温度和延长停留时间,热解气中的H2, CH4和CO产率增加,CO2产率减少,焦油中杂原子化合物及其中的酚、甲酚和二甲酚产率降低,大于3环的重质多环芳烃(PAHs)产率增加,H/C和O/C原子比降低,特别是在900℃时,随停留时间延长,H2和重质PAHs产率快速增加.

本文引用格式

敦启孟 陈兆辉 皇甫林 周杨 余剑 高士秋 刘鸿雁 . 温度和停留时间对煤热解挥发分二次反应的影响[J]. 过程工程学报, 2018 , 18(1) : 140 -147 . DOI: 10.12034/j.issn.1009-606X.217192

Abstract

The influences of temperature and residence time on secondary reactions of coal pyrolysis volatiles were investigated in a dual-stage fixed bed reactor. The results showed that the effects of temperature and residence time on secondary reactions are closely related. The secondary reactions of volatiles hardly occurred in general at the secondary reaction temperature≤600℃ and under residence time 2 s. The tar yield decreased while corresponding gas and deposited carbon yields increased by increasing temperature and residence time due to the intensified secondary reaction of volatiles. At lower temperature (below 700℃), the tar mainly converted into gas product by secondary cracking of tar. At higher temperature (above 700℃), the tar transformed into gas and deposited carbon products by the secondary cracking and coking of tar. With the increase of the temperature and the residence time of secondary reactions, the yields of H2, CH4 and CO increased while CO2 yield decreased, and also lead to the increase of the heavy PAHs (polycyclic aromatic hydrocarbons of more than 3 ring) and the decrease of the phenol, cresol, xylenol and atom ratio of H/C and O/C. Especially at 900℃, the yields of H2 and heavy PAHs increased rapidly with increasing the residence time, due to the occurrence of the violent condensation reactions among aromatic rings.

参考文献

[1]Liu Z Y, Guo X J, Shi L, et al.Reaction of Volatiles–a Crucial Step in Pyrolysis of Coals[J].Fuel, 2015, 154(8):361-369
[2]Chen Z H, Shi Y, Lai D G, et al.Coal Rapid Pyrolysis in a Transport Bed under Steam-Containing Syngas Atmosphere Relevant to the Integrated Fluidized Bed Gasification[J].fuel, 2016, 176:200-208
[3]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].Journal of Chemical Industry and Engineering, 2016, 67(1):1-5
[4]Xu W C, Tomita A.The Effects of Temperature and Residence Time on the Secondary Reactions of Volatiles from Coal Pyrolysis[J].Fuel Processing Technology, 1989, 21(1):25-37
[6]Katheklakis I E, Lu S L, Bartle K D, et al.Effect of Freeboard Residence Time on the Molecular Mass Distributions of Fluidized Bed Pyrolysis Tars[J].Fuel, 1990, 69(2):172-1763
[7]Hayashi J, Nakagawa K, Kusakabe K, et al.Change in Molecular Structure of Flash Pyrolysis Tar by Secondary Reaction in a Fluidized Bed Reactor[J].Fuel Processing Technology, 1992, 30(3):237-248
[8]李海滨,杨之媛,吕红,等.煤在流化床中的热解,: 稀相段温度和停留时间对气体产物组成的影响[J].燃料化学学报, 1998, 26(4):389-344
[9]Li H B, Yang Z Y, Lü H, et al.Pyrolysis of Coal in a Fluidized Bed Reactor,ⅡEffects of Temperature and Residence Time in Freeboard on Gaseous Product Composition[J].Journal of Fuel Chemistry and Technology, 1998, 26(4):389-344
[10]陈昭睿,王勤辉,郭志航,等.热解气停留时间对典型烟煤热解产物的影响[J].热能动力工程, 2015, 30(5):756-761
[11]Chen Z R, Wang Q H, Guo Z H, et al.Influence of the Residence Time of Gases Pyrolyzed on the Pyrolytic Products of Typical Bituminous Coal[J].Journal of Engineering for Thermal Energy and Power, 2015, 30(5):756-7611
[12]Tyler R J.Flash Pyrolysis of CoalsDevolatilization of Bituminous Coals in a Small Fluidized-Bed Reactor[J].Fuel, 1980, 59(4):218-226
[13]石振,成帅,陈兆辉,等.神木烟煤热解产物分布及主要元素的迁移规律[J].过程工程学报, 2016, 16(5):802-811
[14]Shi Z, Cheng S, Chen Z H, et al.Distribution of Products and Migration of Main Elements during Pyrolysis of Shenmu Bituminous Coal[J].The Chinese Journal of Process Engineering, 2016, 16(5):802-811
[15]Li C, Suzuki K.Tar Property,Analysis,Reforming Mechanism and Model for Biomass Gasification–an Overview[J].Renewable & Sustainable Energy Reviews, 2009, 13(3):594-604
[16]Tursun Y, Xu S P, Wang G Y, et al.Tar Formation during CO–Gasification of Biomass and Coal under Different Gasification Condition [J]. Journal of Analytical and Applied Pyrolysis[J].Journal of Analytical and Applied Pyrolysis, 2015, 111:191-199
[17]Xu W C, Tomita A.Effect of Temperature on the Flash Pyrolysis of Various Coals[J].Fuel, 1987, 66(5):632-636
[18]Chen Z H, Dun Q M, Shi Y, et al.High Quality Syngas Production from Catalytic Coal Gasification Using Disposable Ca(OH)2 Catalyst[J].Chemical Engineering Journal, 2017, 316:842-849
[19]Sada E, Kumazawa H, Kudsy M.Pyrolysis of Lignins in Molten Salt Media[J].Industrial & Engineering Chemistry Research, 1992, 31(2):612-616
[20]Mahadevan R, Adhikari S, Shakya R, et al.Effect of Alkali and Alkaline Earth Metals on in-Situ Catalytic Fast Pyrolysis of Lignocellulosic Biomass: a Microreactor Study[J].Energy & Fuels, 2016, 30(4):3045-3056
[21]Jamil K, Hayashi J, Li C Z.Pyrolysis of a Victorian Brown Coal and Gasification of Nascent Char in CO2 Atmosphere in a Wire-mesh Reactor [J]. Fuel, 2004, 83: 833-843.[J].fuel, 2004, 83:833-843
[22]Gao S P, ZHAO J T, Wang Z Q, et al.Effect of CO2 on Pyrolysis Behaviors of Lignite[J].Journal of Fuel Chemistry and Technology, 2013, 41(3):257-264
[23]李海滨,房倚天,王洋,等.二次反应对煤热解产品组成的影响[J].化学工业与工程, 1997, 14(4):45-51
[24]Li H b, Fang Y T, Wang Y, et al.The Effects of Secondary Reaction on the Product Composition of Coal Pyrolysis [J].. 1997, 14(4): 45-51.[J].Chemical Industry and Engineering, 1997, 14:45-51
[25]庄叔贤,季明荣.酚在 上的吸附与分解[J].化学物理学报, 1994, 7(6):558-565
[26]Zhuang S X, Ji M R.Adsorption and Decomposition of Phenol on Pd(110)Surface[J].Chinese Journal of Chemical Physics, 1994, 7(60):558-565
[27]Campbell J H, Koskinas G J, Stout N D, et al.Kinetics of Oil Generation from Colorado Oil Shale[J].Fuel, 1978, 57(6):372-6
[28]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
[29]Chen Z H, Dun Q M, Shi Y, et al.Effects of Pyrolysis Temperature and Atmosphere on Rapid Coal Pyrolysis in a Transport Bed Reactor[J].Journal of Chemical Industry and Engineering, 2017, 68(4):1566-1573
[30]陈兆辉.复合流化床低阶煤气化耦合热解制备富甲烷合成气和焦油 [D]. 北京: 中国科学院大学, 2016.
[31]Chen Z H.Production of Methane–rich Syngas and Tar from Low–rank Coals by Coupling Pyrolysis and Gasification in an Integrated Fluidized Bed [D]. Beijing: University of Chinese Academy of Sciences, 2016.
文章导航

/