Study on the effect of anion and cation for petroleum coke gasification reaction

doi:10.16085/j.issn.1000-6613.2017.06.047

Abstract

Abstract: Petroleum coke is a by-product of ill crude oil processing in refinery and it has a lot of disadvantages as fuel. With the high temperature gasification technology,however,the utilization of petroleum coke can be realized. Based on the existing catalytic gasification reaction mechanism,this paper makes a comparative analysis on the four mainstream mechanisms of petroleum coke gasification reaction. The influences of anion,cation and radical on the gasification reaction mechanisms have been discussed. Also,this paper makes a summary of existing problems and the applicable gasification mechanism for different types of ions. The mechanism of gasification is suitable for single ion catalysis,but not for the phenomenon of complex interaction with different types of ions. Meanwhile,some heavy metal ions in the petroleum coke can inhibit the gasification reactivity of the petroleum coke,and the mechanism has not been studied thoroughly. In conclusion,the interaction between ions in gasification reaction and the influence mechanism of heavy metal ions on gasification reaction will be the focus of future research.

Key words: petroleum coke, catalyst, ion, gasification mechanism, reaction, catalysis

摘要： 石油焦是炼厂劣质原油加工的副产物，其作为燃料来说具有较多的不足之处。利用高温气化技术可以实现石油焦的资源化再利用。文中对4种主流的气化反应机理进行对比分析，并结合现有的催化气化理论对气化反应过程中阴、阳离子及自由基对气化反应的影响机制进行讨论，对不同种类离子所适用的气化反应机理加以分类总结并指出存在的问题。指出阴、阳离子对石油焦气化反应影响较大，气化机理对于单一类型离子催化过程的作用机制解释较为合理，但对于不同种类离子复合后相互作用的现象解释不通。同时，石油焦中所含的一些重金属离子会抑制石油焦的气化反应活性，机理对于上述现象也并未深入研究。在此基础上，提出了气化反应中离子间的相互作用及重金属离子对气化反应的影响机理将是今后的研究重点。

关键词: 石油焦, 催化剂, 离子, 气化机理, 反应, 催化作用

CLC Number:

TQ546

LU Lei, XU Hao, ZHAO Dongfeng. Study on the effect of anion and cation for petroleum coke gasification reaction[J]. Chemical Industry and Engineering Progress, 2017, 36(06): 2298-2303.

卢磊, 徐浩, 赵东风. 阴、阳离子对石油焦气化反应的影响[J]. 化工进展, 2017, 36(06): 2298-2303.

References

[1] SALVADOR S,COMMANDRÉ J M,STANMORE B R. Reaction rates for the oxidation of highly sulphurized petroleum cokes:the influence of thermogravimetric conditions and some coke properties [J]. Fuel,2003,82(6):715-720.
[2] 罗艳托. 石油焦市场发展趋势概述[J]. 石油规划设计,2008,19(6):10-11. LUO Y T. Development trend of petroleum coke market[J]. Petroleum Planning & Engineering,2008,19(6):10-11.
[3] 吴正舜,张春林,陈汉平,等. 石油焦的燃烧特性[J]. 化工学报,2001,52(9):834-837. WU Z S,ZHANG C L,CHEN H P,et al. Combustion characteristics of petroleum[J]. Journal of Chemical Industry and Engineering,2001,52(9):834-837.
[4] NILSSON S,GÓMEZ-BAREA A,CANO D F. Gasification reactivity of char from dried sewage sludge in a fluidized bed[J]. Fuel,2012,92(1):346-353.
[5] 盖希坤,毛建卫,杨瑞芹,等. 生物质半焦气化反应的研究进展[J]. 现代化工,2014,34(3):45-49. GE X K,MAO J W,YANG R Q,et al. Research progress of gasification reaction with biomass[J]. Modern Chemical Industry,2014,34(3):45-49.
[6] 张保申,刘鑫,周志杰,等. 微波活化对石油焦气化特性的影响[J]. 石油学报(石油加工),2011,27(4):555-560. ZHANG B S,LIU X,ZHOU Z J,et al. Effect of microwave activation on gasification properties of petroleum coke[J]. Acta Petrolei Sinica (Petroleum Processing Section),2011,27(4):555-560.
[7] 郝巧铃,白永辉,李凡. 生物质与煤共气化特性的研究进展[J]. 化工进展,2011,30(s1):68-70. HAO Q L,BAI Y H,LI F. Research progress on co-gasification characteristics of biomass and coal[J]. Chemical Industry and Engineering Progress,2011,30(s1):68-70.
[8] 王辅臣,于广锁,龚欣,等. 大型煤气化技术的研究与发展[J]. 化工进展,2009,28(2):173-180. WANG F C,YU G S,GONG X,et al. Research and development of large coal gasification technology[J]. Chemical Industry and Engineering Progress,2009,28(2):173-180.
[9] 汪寿建. 现代煤气化技术发展趋势及应用综述[J]. 化工进展,2016,35(3):653-664. WANG S J. Development trend and application of modern coal gasification technology[J]. Chemical Industry and Engineering Progress,2016,35(3):653-664.
[10] LIU X,ZHOU Z,ZHANG B,et al. Effect of microwave treatment on structural changes and gasification reactivity of petroleum coke[J]. Industrial & Engineering Chemistry Research,2011,50(15):9063-9068.
[11] 吴诗勇,吴幼青,顾菁,等. 高温煅烧条件下石油焦和沥青焦的物理结构及其CO₂气化特性[J]. 石油学报(石油加工),2009,25(2):258-265. WU S Y,WU Y Q,GU J,et al. Physical structure and CO₂ gasification characteristics of petroleum coke and pitch coke under high temperature calcination[J]. Acta Petrolei Sinica (Petroleum Processing Section),2009,25(2):258-265.
[12] 胡启静. 铁系催化剂对煤和石油焦气化影响的研究[D]. 上海:华东理工大学,2012. HU Q J. Effect of iron species on the gasification of coal and petroleum coke[D]. Shanghai:East China University of Science and Technology,2012.
[13] 熊杰,周志杰,许慎启,等. 碱金属对煤热解和气化反应速率的影响[J]. 化工学报,2011,62(1):192-198. XIONG J,ZHOU Z J,XU S Q,et al. Effect of alkali metals on coal pyrolysis and gasification reaction rate[J]. Journal of Chemical Industry and Engineering,2011,62(1):192-198.
[14] JIE W,YAO Y,CAO J,et al. Enhanced catalysis of K₂CO₃ for steam gasification of coal char by using Ca(OH)₂ in char preparation[J]. Fuel,2010,89(2):310-317.
[15] WANG J,JIANG M,YAO Y,et al. Steam gasification of coal char catalyzed by K₂CO₃ for enhanced production of hydrogen without formation of methane[J]. Fuel,2009,88(9):1572-1579.
[16] 周晨亮,刘全生,李阳,等. 胜利褐煤水蒸气气化制富氢合成气及其固有矿物质的催化作用[J]. 化工学报,2013,64(6):2092-2102. ZHOU C L,LIU Q S,LI Y,et al. Catalytic action of Shengli lignite steam gasification to produce hydrogen-rich syngas and its inherent minerals[J]. Journal of Chemical Industry and Engineering(China),2013,64(6):2092-2102.
[17] 方梦祥,厉文榜,岑建孟,等. 煤催化气化技术的研究现状与展望[J]. 化工进展,2015,34(10):3656-3664. FANG M X,LI W B,CEN J M,et al. Research status and prospect of coal catalytic gasification technology[J]. Chemical Industry and Engineering Progress,2015,34(10):3656-3664.
[18] SANCIER K M. Effects of catalysts and steam gasification on e.s.r. of carbon black[J]. Fuel,1983,62(3):331-335.
[19] WOOD B J,FLEMING R H,WISE H. Reactive intermediate in the alkali-carbonate-catalysed gasification of coal char[J]. Fuel,1984,63(11):1600-1603.
[20] WEN W Y. Mechanisms of alkali metal catalysis in the gasification of coal,char,or graphite[J]. Catalysis Reviews,1980,22(1):399-401.
[21] RAO Y,ADJORLOLO A,HABERMAN J. On the mechanism of catalysis of the Boudouard reaction by alkali-metal compounds[J]. Carbon,1982,20(3):207-212.
[22] MCKEE D W. Mechanisms of the alkali metal catalysed gasification of carbon[J]. Fuel,1983,62(2):170-175.
[23] 盖希坤,卢艺,杨瑞芹,等. 碳-水蒸气气化反应新机理探讨[J]. 化学世界,2015,56(8):491-495. GE X K,LU Y,YANG R Q,et al. Discussion on new mechanism of carbon-water vaporization reaction[J]. Chemical World,2015,56(8):491-495.
[24] 潘英刚,刘敏芝,计承仪,等. 煤加压催化气化研制城市煤气——Ⅰ. 大同煤和煤焦的催化气化特性[J]. 华东理工大学学报,1986(1):28-36. PAN Y G,LIU M Z,JI C Y,et al. Development of urban gas by pressurized coal gasification——Ⅰ. Catalytic gasification characteristics of Datong Coal[J]. Journal of East China University,1986(1):28-36.
[25] 杜留娟,王许云. 催化气化(一步法)煤制天然气催化剂研究进展[J]. 当代化工,2015(6):1332-1335. DU L J,WANG X Y. Research progress of catalytic gasification (one step)catalyst for coal natural gas[J]. Contemporary Chemical Industry,2015(6):1332-1335.
[26] 赵新法,杨黎燕,石振海. 煤中矿物质在气化反应中的催化作用分析[J]. 煤炭技术,2005,24(1):103-105. ZHAO X F,YANG L Y,SHI Z H. Catalysis of coal minerals in gasification reaction[J]. Coal Technology,2005,24(1):103-105.
[27] 郭培民,张临峰,赵沛. 碳气化反应的催化机理研究[J]. 钢铁,2008,43(2):26-30. GUO P M,ZHANG L F,ZHAO P. Catalytic mechanism of carbon gasification reaction[J]. Iron and Steel,2008,43(2):26-30.
[28] CHEN S G,YANG R T. Unified mechanism of alkali and alkaline earth catalyzed gasification reactions of carbon by CO₂ and H₂O[J]. Energy & Fuels,1997,11(2):421-427.
[29] 刘鑫. 热处理及金属催化对石油焦气化过程的影响研究[D]. 上海:华东理工大学,2012. LIU X. Effect of heat treatment and metal catalysis on gasification process of petroleum coke[D]. Shanghai:East China University of Science and Technology,2012.
[30] 余维高. 生物质与石油焦共气化特性研究[D]. 杭州:浙江大学,2013. YU W G. Study on co-gasification of biomass and petroleum coke[D]. Hangzhou:Zhejiang University,2013.
[31] YU J,TIAN F J,CHOW M C,et al. Effect of iron on the gasification of Victorian brown coal with steam:enhancement of hydrogen production[J]. Fuel,2006,85(2):127-133.
[32] 程煜,刘永卓,田红景,等. 铁基复合载氧体煤化学链气化反应特性及机理[J]. 化工学报,2013,64(7):2587-2595. CHENG Y,LIU Y Z,TIAN H J,et al. Characteristics and mechanism of chemical chain gasification reaction of Fe-based composite carrier oxygen[J]. Journal of Chemical Industry and Engineering(China),2013,64(7):2587-2595.
[33] JIANG M Q,RONG Z,JIE H,et al. Calcium-promoted catalytic activity of potassium carbonate for steam gasification of coal char:influences of calcium species[J]. Fuel,2012,99(9):64-71.
[34] RADOVIC L R. Catalytic coal gasification:use of calcium versus potassium[J]. Fuel,1984,63(7):1028-1030.
[35] GONZÁLEZ J D,MONDRAGÓN F,ESPINAL J F. Effect of calcium on gasification of carbonaceous materials with CO₂:a DFT study[J]. Fuel,2013,114(6):199-205.
[36] LANG R J. Anion effects in alkali-catalyzed steam gasification [J]. Fuel,1986,65(10):1324-1329.
[37] 陈凡敏. 碳酸钾对煤水蒸气气化反应性影响的研究[D]. 上海:华东理工大学,2013. CHEN F M. Study on influence of potassium carbonate to gasification of coal with steam[D]. Shanghai:East China University of Science and Technology,2013.