热解气氛与温度对褐煤半焦“一步法”甲烷化活性的影响

doi:10.16085/j.issn.1000-6613.2016-2259

化工进展 ›› 2017, Vol. 36 ›› Issue (10): 3690-3696.DOI: 10.16085/j.issn.1000-6613.2016-2259

热解气氛与温度对褐煤半焦“一步法”甲烷化活性的影响

岳永强, 刘永卓, 常国璋, 郭庆杰

青岛科技大学化工学院, 清洁化工过程山东省高校重点实验室, 山东青岛 266042

收稿日期:2016-12-06 修回日期:2017-02-15 出版日期:2017-10-05 发布日期:2017-10-05
通讯作者: 郭庆杰,教授.
作者简介:岳永强(1991-),男,硕士研究生.
基金资助:
国家自然科学基金（21276129，51506105）、山东省自然科学基金重点项目（ZR2015QZ02）及山东省自然科学基金（ZR2015BL028）项目。

Influence of pyrolysis atmosphere and temperature on “one step” methanation activity of lignite semi-coke

YUE Yongqiang, LIU Yongzhuo, CHANG Guozhang, GUO Qingjie

Key Laboratory of Clean Chemical Processing of Shandong Province, School of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, Shandong, China

Received:2016-12-06 Revised:2017-02-15 Online:2017-10-05 Published:2017-10-05

摘要/Abstract

摘要： 为提高褐煤热解多联产技术中半焦的利用效率，本文提出将低温热解半焦用于"一步法"制甲烷技术，考察了热解条件对半焦性质和一步甲烷化活性的影响。利用管式炉制备了不同气氛和温度的褐煤热解半焦，采用傅里叶红外光谱、X射线衍射技术和固定床反应器，对半焦表面化学、微晶结构和甲烷化活性进行了表征。结果表明，与N₂和H₂氛围相比，褐煤在水蒸气氛围中进行热解，半焦表面含氧官能团受到保护而含量更高，同时石墨化程度因受阻而降低，甲烷化活性更高；在水蒸气氛围中，773～873K范围内，随着热解温度升高，褐煤裂解反应进行程度加深，半焦表面含氧官能团数量降低，石墨化程度增加，致使甲烷化活性降低。总之，在水蒸气氛围中，773K时热解形成了一步甲烷化反应活性最好的褐煤半焦，对于低阶褐煤热解过程与气化过程优化联产具有重要指导意义。

关键词: 热解条件, 褐煤半焦, 甲烷化, 一步法

Abstract: To improve the semi-cokes utilization efficiency in multi generation technology of coal pyrolysis,the application of low temperature pyrolysis char to methane by one step process was proposed. The influence of pyrolysis conditions on"one step"methanation activity was investigated in this work. A series of semi-coke samples derived from pyrolysis of Erdos lignite were prepared grammed under different atmosphere and temperature using a tubular furnace. The surface chemical,microcrystalline structure and methanation activity of these semi-cokes were investigated by means of Fourier transform infrared spectrometer(FTIR),X-ray diffraction (XRD) and a fixed-bed reactor. The results demonstrated that the interaction of H₂O with the lignite could weaken the loss of the oxygen-containing functional groups and restrain the graphitization process of semi-cokes. Thereby,the semi-cokes with higher content of oxygen-containing functional groups and lower graphitization degree were observed under H₂O ambiance compared with those in N₂ and H₂ atmosphere. In the range of 773K to 873K under H₂O atmosphere,the pyrolysis reaction proceeded more deeply with increasing temperature,which led to fewer oxygen functional groups and higher graphitization degree in the semi-cokes. As a result,the CH₄ accumulation was reduced. The optimal pyrolysis condition for methanation reactivity was under H₂O atmosphere at 773K,which was of great significance to optimize the co-production of pyrolysis and gasification process of low rank lignite.

Key words: pyrolysis condition, lignite semi-coke, methanation, one step method

中图分类号:

TQ546.1

岳永强, 刘永卓, 常国璋, 郭庆杰. 热解气氛与温度对褐煤半焦“一步法”甲烷化活性的影响[J]. 化工进展, 2017, 36(10): 3690-3696.

YUE Yongqiang, LIU Yongzhuo, CHANG Guozhang, GUO Qingjie. Influence of pyrolysis atmosphere and temperature on “one step” methanation activity of lignite semi-coke[J]. Chemical Industry and Engineering Progress, 2017, 36(10): 3690-3696.

参考文献

[1] BP.BP statistical review of world energy 2015[R].London,BP,2015.
[2] ZHANG C,HE X,ZHU S,et al.Distribution,character and utilization of lignite in China[C]//Power & Energy Engineering Conference,2011:1-4.
[3] AMELIO M,MORRONE P,GALLUCCI F,et al.Integrated gasification gas combined cycle plant with membrane reactors:technological and economical analysis[J].Energy Conversion & Management,2007,48(10):2680-2693.
[4] 岑建孟,方梦祥,王勤辉,等.煤分级利用多联产技术及其发展前景[J].化工进展,2010,29(s1):705-712.CEN Jianmeng,FANG Mengxiang,WANG Qinhui,et al.Development and prospect of coal staged conversion poly-generation technology[J].Chemical Industry and Engineering Progress,2010,29(s1):705-712.
[5] REGNERY J A,SHEPPARD R O.Integration of an integrated gasification combined cycle power plant and coal to liquid facility:US8105403B2[P].2012-01-31.
[6] 范晓雷,周志杰,王辅臣,等.热解条件对煤焦气化活性影响的研究进展[J].煤炭转化,2005,28(3):74-79.FAN Xiaolei,ZHOU Zhijie,WANG Fuchen,et al.Study on influence of pyrolysis conditions on char gasification reactivity[J].Coal Conversion,2005,28(3):74-79.
[7] 白少锋,郭庆杰,徐秀峰.煤"一步法"制天然气催化剂[J].化工学报,2014,65(8):2988-2996.BAI Shaofeng,GUO Qingjie,XU Xiufeng.Catalyst for one-step production of synthetic natural gas from coal[J].CIESC Journal,2014,65(8):2988-2996.
[8] KOPYSCINSKI J,SCHILDHAUER T J,BIOLLAZ S M A.Production of synthetic natural gas(SNG)from coal and dry biomass-A technology review from 1950 to 2009[J].Fuel,2010,89(8):1763-1783.
[9] HEEK K H V.Progress of coal science in the 20th century[J].Fuel,2000,79(1):1-26.
[10] HIRSCH R L,GALLAGHER J E,LESSARD R R,et al.Catalytic coal gasification:an emerging technology[J].Science,1982,215(4529):121-7.
[11] 张永发,王影,丁晓阔,等.一种制备甲烷化碳材料的方法:102676190A[P].2012-09-19.ZHANG Yongfa,WANG Ying,DING Xiaokuo,et al.Method for preparing methanation carbon materials:102676190A[P].2012-09-19.
[12] 张天开,张永发,王琪,等.褐煤半焦直接加氢制甲烷反应特性及其孔结构和表面形态变化[J].燃料化学学报,2015,43(3):289-301.ZHANG Tiankai,ZHANG Yongfa,WANG Qi,et al.Hydrogasification of lignite semicoke to produce methane and the textural properties of coke residues[J].Journal of Fuel Chemical and Technology,2015,43(3):289-301.
[13] WIKTORSSON L P,WANZL W,WIKTORSSON L P,et al.Kinetic parameters for coal pyrolysis at low and high heating rates-a comparison of data from different laboratory equipment[J].Fuel,2000,79(6):701-716.
[14] YAN B H,CAO C X,CHENG Y,et al.Experimental investigation on coal devolatilization at high temperatures with different heating rates[J].Fuel,2014,117(1):1215-1222.
[15] 冯杰,李文英,谢克昌.傅立叶红外光谱法对煤结构的研究[J].中国矿业大学学报,2002,31(5):362-366.FENG Jie,LI Wenying,XIE Kechang.Study on the structure of coal by FT-IR[J].Journal of China University of Minning & Technology,2002,31(5):362-366.
[16] 赵冰,周志杰,丁路,等.快速热处理石油焦与煤的微观结构变化及气化活性分析[J].燃料化学学报,2013,41(1):40-45.ZHAO Bing,ZHOU Zhijie,DING Lu,et al.Changes in the microstructure and gasification reactivity of petroleum coke and coal samples after rapid pyrolysis[J].Journal of Fuel Chemical and Technology,2013,41(1):40-45.
[17] WIGMANS T,ELFRING R,MOULIJN J A.On the mechanism of the potassium carbonate catalysed gasification of activated carbon:the influence of the catalyst concentration on the reactivity and selectivity at low steam pressures[J].Carbon,1983,21(1):1-12.
[18] 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.
[19] KIM J,CHOI H,LIM J,et al.Hydrogen production via steam gasification of ash free coals[J].International Journal of Hydrogen Energy,2013,38(14):6014-6020.
[20] KOPYSCINSKI J,LAM J,MIMS C A,et al.K₂CO₃ catalyzed steam gasification of ash-free coal.Studying the effect of temperature on carbon conversion and gas production rate using a drop-down reactor[J].Fuel,2014,128(14):210-219.
[21] 解强,梁鼎成,田萌,等.升温速率对神木煤热解半焦结构性能的影响[J].燃料化学学报,2015,43(7):798-805.XIE Qiang,LIANG Dingcheng,TIAN Meng,et al.Influence of heating rate on structure of chars derived from pyrolysis of Shenmu coal[J].Journal of Fuel Chemical and Technology,2015,43(7):798-805.
[22] 解强,边炳鑫.煤的炭化过程控制理论及其在煤基活性炭制备中的应用[M].徐州:中国矿业大学出版社,2002.XIE Qiang,BIAN Bingxin.Coal carbonization process control theory and its application in the preparation of coal based activated carbon[M].Xuzhou:China University of Mining and Technology Press,2002.
[23] 谢克昌.煤的结构与反应性[M].北京:科学出版社,2002.XIE Kechang.Structure and reactivity of coal[M].Beijing:Science Press,2002.
[24] LU L,SAHAJWALLA V,KONG C,et al.Quantitative X-ray diffraction analysis and its application to various coals[J].Carbon,2001,39(12):1821-1833.

热解气氛与温度对褐煤半焦“一步法”甲烷化活性的影响

Influence of pyrolysis atmosphere and temperature on “one step” methanation activity of lignite semi-coke

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	马源, 肖晴月, 岳君容, 崔彦斌, 刘姣, 许光文. CeO₂-Al₂O₃复合载体负载Ni基催化剂催化CO _x 共甲烷化性能[J]. 化工进展, 2023, 42(5): 2421-2428.
[2]	张巍, 王锐, 缪平, 田戈. 全球可再生能源电转甲烷的应用[J]. 化工进展, 2023, 42(3): 1257-1269.
[3]	张玉黎, 叶茂, 肖睿, 葛立超. 垃圾焚烧发电耦合电转气制备合成天然气工艺集成与优化[J]. 化工进展, 2022, 41(3): 1677-1688.
[4]	纪子柯, 包成. CO选择性甲烷化的研究进展[J]. 化工进展, 2022, 41(1): 120-132.
[5]	王国栋, 郭亚飞, 李佳媛, 姚睿璇, 孙健, 赵传文. 碱/碱土金属修饰Ni基催化剂的CO₂吸附与甲烷化性能[J]. 化工进展, 2021, 40(12): 6925-6933.
[6]	毕荣山, 张艳, 陈彦臻, 孙映辉, 陈伦波, 王明泽, 夏力, 孙晓岩, 项曙光. 异戊烷一步脱氢制备异戊二烯工艺模拟分析及经济评价[J]. 化工进展, 2021, 40(11): 5961-5966.
[7]	宫万福,闫兵海. 新型VESTA甲烷化工艺路线探究[J]. 化工进展, 2020, 39(1): 112-118.
[8]	孙漪清, 金保昇, 董新新, 张文杰, 王金德. ZrO₂-Al₂O₃复合载体负载Ni基催化剂CO _x 甲烷化性能[J]. 化工进展, 2019, 38(07): 3176-3184.
[9]	李春启. 新型合成气甲烷化催化剂La₂O₃-ZrO₂-Ni /Al₂O₃的制备与性能[J]. 化工进展, 2019, 38(06): 2776-2783.
[10]	杨霞, 秦绍东, 李加波, 孙守理. 载体制备方法对MoO₃/ZrO₂耐硫甲烷化催化剂的影响[J]. 化工进展, 2017, 36(04): 1288-1293.
[11]	李春启. 基于动力学模型的合成气完全甲烷化回路系统模拟分析[J]. 化工进展, 2017, 36(01): 146-155.
[12]	杨霞, 秦绍东, 李加波, 孙守理. ZrO₂添加对MoO₃/Al₂O₃催化剂耐硫甲烷化性能的影响[J]. 化工进展, 2016, 35(S2): 179-182.
[13]	张旭, 王子宗, 陈建峰. 煤基合成气甲烷化用镍基催化剂失活热力学和抗失活预测[J]. 化工进展, 2016, 35(11): 3511-3518.
[14]	褚睿智, 徐婷婷, 孟献梁, 吴国光, 侯文心. 助剂对Pd/γ-Al₂O₃催化剂一步法合成二甲醚反应稳定性的影响[J]. 化工进展, 2016, 35(08): 2474-2479.
[15]	林凤采, 卢麒麟, 林咏梅, 庄森炀, 李现艳, 黄彪. 一步法制备乙酰化纳米纤维素及其性能表征[J]. 化工进展, 2016, 35(02): 559-564.