合成气一步法制备液化石油气单管实验研究

吕永兴; 徐海燕; 周意; 陈坚; 吴创之

合成气一步法制备液化石油气单管实验研究

1.
中国科学院广州能源研究所中国科学院可再生能源重点实验室, 广东广州 510640;
2.
中国科学院大学, 北京 100049;
3.
河南省科学院能源研究所有限公司河南省生物质能源重点实验室, 河南郑州 450008

基金项目: 国家科技支撑计划(2012BAA09B03); 广东省战略新兴产业项目(2012A032300019)。

详细信息

通讯作者:
吴创之,Tel:020-87057688,E-mail:wucz@ms.giec.a.cn。

中图分类号: TQ517.2
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出版历程
- 收稿日期: 2014-08-15
- 刊出日期: 2015-03-30

Direct synthesis of LPG from syngas in a single-tube reactor

1.
Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China;
2.
University of Chinese Academy of Sciences, Beijing 100049, China;
3.
Energy Research Institute Co., Ltd of Henan Academy of Sciences, Key Biomass Energy Lab of Henan Province, Zhengzhou 450008, China

摘要

摘要: 采用甲醇合成催化剂与脱水催化剂机械混合,制备了液化石油气(LPG)合成催化剂。以模拟生物质气为原料气,在固定床单管实验装置上,温度(220~330 ℃)、压力(1.2~5.1 MPa)和空速(500~3 000 h^-1)条件下考察催化剂的性能。结果表明,在325 ℃、2.1 MPa、1 500 h^-1条件下,CO转化率达到72.36%,LPG占烃类产物的71.21%。当设定温度为325 ℃、压力2.1 MPa时、空速≤2 500 h^-1时,系统可以稳定运行;空速达到3 000 h^-1时,反应器内部温度迅速升高无法控制,造成催化剂烧结失活。针对上述催化剂,采用NH₃-TPD、XRD、N₂吸附-脱附和TPO对催化剂进行了表征。结果表明,催化剂的积炭、强酸位酸性降低及比表面积的降低是导致催化剂活性降低的重要影响因素。
- 合成气 /
- 液化石油气 /
- 复合催化剂 /
- 失活 /
- 积炭
Abstract: A hybrid catalyst for the direct synthesis of liquefied petroleum gas (LPG) from syngas was prepared through mechanical mixing of methanol synthesis catalyst with dehydration catalyst; its catalytic performance was tested in a single-tube reactor with a simulated biogas at 220~330 ℃, 1.2~5.1 MPa and a space velocity of 500~3 000 h^-1. The results indicated that the hybrid catalyst has a good activity; at 325 ℃, 2.1 MPa, and a space velocity of 1 500 h^-1, CO conversion and LPG content in the hydrocarbons product are 72.36% and 71.21%, respectively. At 325 ℃ and 2.1 MPa, a stable operation can be realized at a space velocity below 2 500 h^-1, whereas the temperature cannot be well controlled at a space velocity over 3 000 h^-1, which may lead to the catalyst deactivation. The NH₃-TPD, XRD, N₂ sorption and TPO characterization results suggest that the deposition of coke and decrease of the mount of strong acid sites and surface area are responsible for the catalyst deactivation.
- syngas /
- liquefied petroleum gas /
- hybrid catalyst /
- catalyst deactivation /
- coke deposition

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参考文献(16)

刘华敏, 马明国, 刘玉兰. 预处理技术在生物质热化学转化中的应用[J]. 化学进展, 2014, 26(1): 203-213.(LIU Hua-min, MA Ming-guo, LIU Yu-lan. Applications of pretreatment in biomass thermo-chemical conversion technology[J]. Prog Chem, 2014, 26(1): 203-213.)

HAMELINCK C N, FAAIJ P C. Future prospects for production of methanol and hydrogen from biomass[J]. J Pow Sources, 2002, 111(1): 1-22.

ASAMI K, ZHANG Q, LI X H, ASAOKA S, FUJIMOTO K. Selective synthesis of LPG from synthesis gas[J]. Stud Surf Sci Catal, 2004, 147: 427-432.

ZHANG Q, LI X, ASAMI K, ASAOKA S, FUJIMOTO K. A highly stable and efficient catalyst for direct synthesis of LPG from syngas[J]. Catal Lett, 2005, 102(1/2): 51-55.

GE Q J, LI X H, FUJIMOTO K. Application of modified beta zeolite in the direct synthesis of LPG from syngas[J]. Stud Surf Sci Catal, 2007, 170: 1260-1266.

ZHANG Q W, LI X H, ASAMI K, ASAOKA S, FUJIMOTO K. Synthesis of LPG from synthesis gas[J]. Fuel Process Technol, 2004, 85: 1139-1150.

ZHANG Q W, LI X H, ASAMI K, ASAOKA S, FUJIMOTO K. Direct synthesis of LPG fuel syngas with the hybrid catalyst based on modified Pd/SiO₂ and zeolite[J]. Catal Today, 2005, 104(1): 30-36.

GE Q J, LI X H, KANEKO H, FUJIMOTO K. Direct synthesis of LPG from synthesis gas over Pd-Zn-Cr/Pd-β hybrid catalysts[J]. J Mol Catal A: Chem, 2007, 278(1/2): 215-219.

GE Q J, LIAN Y, YUAN X H, LI X H, FUJIMOTO K. High perfor-mance Cu-ZnO/Pd-β catalysts for syngas to LPG[J]. Catal Commun, 2008, 9(2): 256-261.

MA X G, GE Q J, MA Y C, XU H Y. Synthesis of LPG via DME from syngas in two-stage reaction system[J]. Fuel Process Technol, 3013, 109: 1-6.

马现刚, 葛庆杰, 方传艳, 马俊国, 徐恒泳. 合成气制液化石油气复合催化剂的性能[J]. 催化学报, 2010, 31(12): 1501-1506.(MA Xian-gang, GE Qing-jie, FANG Chuan-yan, MA Jun-guo, XU Heng-yong. Hybrid Catalysts for Liquefied Petroleum Gas Synthesis from Syngas[J]. Chin J Catal, 2010, 31(12): 1501-1506.)

马现刚, 葛庆杰, 徐恒泳. 复合催化剂上合成气一步法制备液化石油气的研究[J]. 燃料化学学报, 2013, 41(8): 1010-1014.(MA Xian-gang, GE Qing-jie, XU Heng-yong. Direct synthesis of liquefied petroleum gas from syngas over hybrid catalyst[J]. J Fuel Chem Technol, 2013, 41(8): 1010-1014.)

LÜ Y X, WANG T J, WU C Z, MA L L, ZHOU Y. Scale study of direct synthesis of dimethyl ether from biomass synthesis gas[J]. Biotechnol Adv, 2009, 27(5): 551-554.

吕永兴, 王铁军, 李宇萍, 吴创之, 马隆龙.生物质合成气一步合成LPG的实验研究.燃料化学学报, 2008, 36(2): 246-249.(LÜ Yong-xing, WANG Tie-jun, LI Yu-ping, WU Chuang-zhi, MA Long-long. Direct synthesis of liquefied petroleum gas from biomass synthesis gas[J]. J Fuel Chem Technol, 2008, 36(2): 246-249.)

LI Y P, WANG T J, YIN X L, WU C Z, MA L L, LI H B, SUN L. Design and operation of integrated pilot-scale dimethyl ether synthesis system via pyrolysis/gasification of corncob[J]. Fuel, 2009, 88(11): 2181-2187.

SOTIROPOULOS A, MILLIGAN P K, COWIE B C C, KADODWALA M. A structural study of formate on Cu(111)[J]. Surf Sci, 2000, 444(1/3): 52-60.

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