Effect of CO<sub>2</sub> in syngas on methanation performance of Mo-based catalyst

LI Zhen-hua; QU Jiang-lei; WANG Wei-han; WANG Bao-wei; MA Xin-bin

Volume 44 Issue 8

Aug. 2016

Turn off MathJax

Article Contents

Article Navigation > Journal of Fuel Chemistry and Technology > 2016 > 44(8): 985-992

LI Zhen-hua, QU Jiang-lei, WANG Wei-han, WANG Bao-wei, MA Xin-bin. Effect of CO2 in syngas on methanation performance of Mo-based catalyst[J]. Journal of Fuel Chemistry and Technology, 2016, 44(8): 985-992.

Citation:

LI Zhen-hua, QU Jiang-lei, WANG Wei-han, WANG Bao-wei, MA Xin-bin. Effect of CO₂ in syngas on methanation performance of Mo-based catalyst[J]. Journal of Fuel Chemistry and Technology, 2016, 44(8): 985-992.

Citation:

PDF( 5515 KB)

Effect of CO₂ in syngas on methanation performance of Mo-based catalyst

Key Lab for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

More Information

Corresponding author: Tel: 021-23500806, E-mail: wangwh@tju.edu.cn; xbma@tju.edu.cn
Received Date: 2016-02-29
Rev Recd Date: 2016-04-23

Available Online: 2021-01-23

Publish Date: 2016-08-10

Abstract

Abstract

The methanation of synthesis gas is the key process of coal to natural gas. Considering the existence of CO₂ in the synthesis gas, it is important to investigate the influence of CO₂ on the sulfur-resistant methanation. In this paper, the effect of CO₂ on methanation activity of Mo-based catalysts was investigated at the reaction temperature of 550℃ and the gas space velocity of 5000h^-1 with the syngas containing 1.2% H₂S (volume ratio). The results show that the promoter Co and the cerium-aluminum composite support can improve the stability of the catalyst and reduce the deactivation. The CO₂ is proved to promote the reverse water gas shift reaction, which would inhibit the activity of MoO₃/Al₂O₃ catalyst more heavily than MoO₃-CoO/CeO₂-Al₂O₃ catalyst. When the CO₂ adding to the inlet gas is less than 10% for 20h, the catalyst activity could be restored to its original activity after stopping the addition of CO₂. However, as the added CO₂ in inlet gas is over 10%, more H₂O will be generated through reverse water gas shift reaction to damage the catalyst structure and decrease the active component, resulting in an irreversible loss of catalyst activity.
- sulfur-resistant methanation,
- Mo-based catalyst,
- carbon dioxide,
- deactivation,
- water-gas shift

FullText(HTML)

References(28)

References

[1]	张东柯.面对人类社会可持续发展的能源选择[J].燃料化学学报, 2005, 33(4):399-406. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract16583.shtml ZHANG Dong-ke.Energy options in sustainable development[J].J Fuel Chem Technol, 2005, 33(4):399-406. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract16583.shtml
[2]	胡亮华, 冯再南, 姚泽龙, 刘维, 申屠梁, 王俊峰.焦炉煤气甲烷化工艺过程的Aspen Plus模拟[J].天然气化工, 2013, 38(3):53-57. http://www.cnki.com.cn/Article/CJFDTOTAL-TRQH201303013.htm HU Liang-hua, FENG Zai-nan, YAO Ze-long, LIU Wei, SHEN Tu-liang, WANG Jun-feng.Aspen Plus simulation of coke oven gas methanation process[J].Nat Gas Ind, 2013, 38(3):53-57. http://www.cnki.com.cn/Article/CJFDTOTAL-TRQH201303013.htm
[3]	SABATIER P, SENDERENS J B.New synthesis of methane[J].CR Acad Sci Paris, 1902, 134:514-516.
[4]	SABATIER P, SENDERENS J B.Hydrogenation of CO over nickel to produce methane[J].J Soc Chim Ind, 1902, 21:504-506.
[5]	黄国宝, 王志青, 李庆峰, 黄戒介, 房倚天, 液相中镍催化剂催化合成气甲烷化的初步研究[J].燃料化学学报, 2014, 42(8):952-957. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18470.shtml HUANG Guo-bao, WANG Zhi-qing, LI Qing-feng, HUANG Jie-jie, FANG Yi-tian.Syngas methanation over nickel catalyst in liquid-phase[J].J Fuel Chem Technol, 2014, 42(8):952-957. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18470.shtml
[6]	MINCHENER A J.Coal gasification for advanced power generation[J].Fuel, 2005, 84(17):2222-2235. doi: 10.1016/j.fuel.2005.08.035
[7]	SCHILDHAUER T J, SEEMANN M C, BIOLLAZ S M A.Fluidized bed methanation of wood-derived producer gas for the production of synthetic natural gas[J].Ind Eng Chem Res, 2010, 49(15):7034-7038. doi: 10.1021/ie100510m
[8]	吴且毅, 卿涛, 颜智.一种利用焦炉气合成甲烷的方法:中国, 101391935 A[P].2009-03-25. WU Qie-yi, QIN Tao, YAN Zhi.Method for synthesizing methane by using coke-oven gas:CN, 101391935 A[P].2009-03-25.
[9]	黄明金, 郭成宇, 尹明大.一种合成氨原料气甲烷化工艺:中国, 1313241 A[P].2001-09-19. HUANG Ming-jin, GUO Cheng-yu, YIN Ming-da.Methanation process for raw gas of synthetic ammonia:CN, 1313241 A[P].2001-09-19.
[10]	GALLETTI C, SPECCHIAS, SARACCO G, SPECCHIA V.CO-selective methanation over Ru/γ-Al₂O₃ catalysts in H₂-rich gas for PEMFC applications[J].Chem Eng Sci, 2010, 65(1):590-596. doi: 10.1016/j.ces.2009.06.052
[11]	徐超, 王兴军, 胡贤辉, 陈雪莉, 王辅臣.镍基催化剂用于合成气甲烷化的实验研究[J].燃料化学学报, 2012, 40(2):216-220. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17886.shtml XU Chao, WANG Xing-jun, HU Xian-hui, CHEN Xue-li, WANG Fu-chen.Study on the syngas methanation of nickel-based catalyst[J].J Fuel Chem Technol, 2012, 40(2):216-220. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17886.shtml
[12]	GAO J J, LIU Q, GU F N, LIU B, ZHONG Z Y, SU F B.Recent advances in methanation catalysts for the production of synthetic natural gas[J].RSC Adv, 2015, 5(29):22759-22776. doi: 10.1039/C4RA16114A
[13]	高聚忠.煤气化技术的应用与发展[J].洁净煤技术, 2013, (1):65-71. http://www.cnki.com.cn/Article/CJFDTOTAL-JJMS201301018.htm GAO Ju-zhong.Application and development of coal gasification technologies[J].Clean Coal Technol, 2013, (1):65-71. http://www.cnki.com.cn/Article/CJFDTOTAL-JJMS201301018.htm
[14]	袁勇天, 尹燕华, 周旭, 周军成.CO、CO₂及其共存体系的甲烷化反应[J].化工进展, 2014, 33(1):173-180. YUAN Yong-tian, YIN Yan-hua, ZHOU Xu, ZHOU Jun-cheng.Methanation of thoree diffenent reaction systems of carbon oxides[J].Chem Ind Eng Process, 2014, 33(1):173-180.
[15]	易丽丽, 马磊, 卢春山, 李小年.CO₂催化加氢甲烷化研究进展[J].化工生产与技术, 2004, 11(5):33-35, 43. YI Li-li, MA Lei, LU Chun-shan, LI Xiao-nian.Study on the catalytic hydrogenation of carbon dioxide for methanation[J].Chem Prod Technol, 2004, 11(5):33-35, 43.
[16]	JIMÉNEZ V, SANCHEZ P, PANAGIOTOPOULOU P, VALVERDE J, ROMERO A.Methanation of CO, CO₂ and selective methanation of CO, in mixtures of CO and CO₂, over ruthenium carbon nanofibers catalysts[J].Appl Catal A:Gen, 2010, 390(1/2):35-44.
[17]	PANAGIOTOPOULOU P, KONDARIDES D, VERKIOS X.Selective methanation of CO over supported noble metal catalysts:Effects of the nature of the metallic phase on catalytic performance[J].Appl Catal A:Gen, 2008, 344(1/2):45-54.
[18]	ECKLE S, ANFANG H, BEHM R.What drives the selectivity for CO methanation in the methanation of CO₂-rich reformate gases on supported Ru catalysts[J].Appl Catal A:Gen, 2011, 391(1):325-333.
[19]	王承学, 龚杰.二氧化碳加氢甲烷化镍锰基催化剂的研究[J].天然气化工, 2011, 36(1):4-15. http://www.cnki.com.cn/Article/CJFDTOTAL-TRQH201101001.htm WANG Cheng-xue, GONG Jie.Study on Ni-Mn-based catalysts for methanation of carbon dioxide[J].Nat Gas Ind, 2011, 36(1):4-15. http://www.cnki.com.cn/Article/CJFDTOTAL-TRQH201101001.htm
[20]	王二东, 王海洋, 丁国忠, 尚玉光, 李振花, 王保伟, 马新宾, 秦绍东, 孙琦.不同工艺条件下耐硫甲烷化催化剂的反应活性研究[J].化学反应工程与工艺, 2012, 28(1):75-81. http://www.cnki.com.cn/Article/CJFDTOTAL-HXFY201201014.htm WANG Er-dong, WANG Hai-yang, DING Guo-zhong, SHANG Yu-guang, LI Zhen-hua, WANG Bao-wei, MA Xin-bin, QIN Shao-dong, SUN Qi.Effect of reaction parameters on the activity of sulfur-resistant methanation catalyst[J].Chem React Eng Technol, 2012, 28(1):75-81. http://www.cnki.com.cn/Article/CJFDTOTAL-HXFY201201014.htm
[21]	LI Z H, WANG H Y, WANG E D, LV J, SHANG Y G, DING G Z, WANG B W, MA X B, QIN S D, SU Q.The main factors controlling generation of synthetic natural gas by methanation of synthesis gas in the presence of sulphur-resistant Mo-based catalysts[J].Kinet Catal, 2013, 54(3):338-343. doi: 10.1134/S0023158413030117
[22]	WANG B W, DING G Z, SHANG Y G, LV J, WANG H Y, WANG E D, LI Z H, MA X B, QIN S D, SUN Q.Effects of MoO₃ loading and calcination temperature on the activity of the sulphur-resistant methanation catalyst MoO₃/γ-Al₂O₃[J].Appl Catal A:Gen, 2012, 431-432(1):144-150.
[23]	LIN C, WANG H Y, LI Z H, WANG B W, MA X B, QIN S D, SUN Q.Effect of a promoter on the methanation activity of Mo-based sulfur-resistant catalyst[J].Front Chem Sci Eng, 2013, 7(1):88-94. doi: 10.1007/s11705-013-1301-1
[24]	王保伟, 尚玉光, 丁国忠, 王海洋, 王二东, 李振花, 马新宾, 秦绍东, 孙琦.铈铝复合载体对钼基催化剂耐硫甲烷化催化性能的研究[J].燃料化学学报, 2012, 40(11):1390-1396. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18073.shtml WANG Bao-wei, SHANG Yu-guang, DING Guo-zhong, WANG Hai-yang, WANG Er-dong, LI Zhen-hua, MA Xin-bin, QIN Shao-dong, SUN Qi.Ceria-alumina composite support on the sulfur-resistant methanation activity of Mo-based catalyst[J].J Fuel Chem Technol, 2012, 40(11):1390-1396. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18073.shtml
[25]	崔晓曦, 曹会博, 孟凡会, 李忠.合成气甲烷化热力学计算分析[J].天然气化工, 2012, 37(5):15-19. http://www.cnki.com.cn/Article/CJFDTOTAL-TRQH201205003.htm CUI Xiao-xi, CAO Hui-bo, MENG Fan-hui, LI Zhong.Thermodynamic analysis for methanation of syngas[J].Nat Gas Ind, 2012, 37(5):15-19. http://www.cnki.com.cn/Article/CJFDTOTAL-TRQH201205003.htm
[26]	陈宏刚, 王腾达, 张锴, 牛玉广, 杨勇平.合成气甲烷化反应积碳过程的热力学分析[J].燃料化学学报, 2013, 41(8):978-984. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18239.shtml CHENG Hong-gang, WANG Teng-da, ZHANG Kai, NIU Yu-guang, YANG Yong-ping.Thermodynamic analysis of carbon deposition on catalyst for the production of substitute natural gas[J].J Fuel Chem Technol, 2013, 41(8):978-984. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18239.shtml
[27]	窦伯生, 谢筱帆, 王玉杰, 石新.Co-Mo-K/Al₂O₃水煤气变换催化剂的失硫与活性[J].石油化工, 1990, (6):387-389. DOU Bo-sheng, XIE Xiao-fan, WANG Yu-jie, SHI Xin.Sulfer loss and activity of Co-Mo-K/Al₂O₃ water gas shift catalyst[J].Petrochem Technol, 1990, (6):387-389.
[28]	LAURENT E, DELMON B.Influence of water in the deactivation of a sulfided NiMo/γ-Al₂O₃ catalyst during hydrodeoxygenation[J].J Catal, 1994, 146(1):281-285, 288-291. doi: 10.1016/0021-9517(94)90032-9