Hβ改性Co/SiO2对费托合成航空燃油类烃的影响

doi:10.3724/SP.J.1077.2014.13479

无机材料学报 ›› 2014, Vol. 29 ›› Issue (6): 599-604.DOI: 10.3724/SP.J.1077.2014.13479 CSTR: 32189.14.SP.J.1077.2014.13479

Hβ改性Co/SiO₂对费托合成航空燃油类烃的影响

李宇萍, 王铁军, 马隆龙, 吴创之, 定明月

(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, 广州 510640)

收稿日期:2013-09-19 修回日期:2013-11-04 出版日期:2014-06-20 网络出版日期:2014-05-27
作者简介:李宇萍(1979–), 女, 副研究员. E-mail:liyp@ms.giec.ac.cn
基金资助:
国家自然科学基金(51006110, 51276183, 51036006);国家自然科学基金中日国际合作项目(51161140331);国家重点基础研究发展计划(973)项目(2013CB228105)

Hβ Modified Co/SiO₂ Catalysts for Fischer-Tropsch Synthesis of Jet Fuel-range Hydrocarbons

LI Yu-Ping, WANG Tie-Jun, MA Long-Long, WU Chuang-Zhi, DING Ming-Yue

(CAS Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China)

Received:2013-09-19 Revised:2013-11-04 Published:2014-06-20 Online:2014-05-27
About author:LI Yu-Ping. E-mail:liyp@ms.giec.ac.cn
Supported by:
National Natural Science Foundation of China((51006110, 51276183, 51036006);National Natural Research Foundation of China/Japan Science and Technology Agency (NSFC/JST, 51161140331);National Key Basic Research Program of China (2013CB228105)

摘要/Abstract

摘要：

在中孔SiO₂(SG)和微孔Hβ分子筛(Si/Al=25、60、80)组成的复合载体上, 制备了多功能Co基费托合成催化剂, 考察了其合成航空燃油类烃(C₈~C₁₈)的性能。XRD、FTIR、H₂-TPR、N₂-物理吸附研究表明: Hβ 的引入, 使得Co/SG/Hβ催化剂具有一定酸性和微孔结构。随分子筛硅铝比的降低, 催化剂红外图谱的特征波数向低波数移动, 酸性有所提高, 中孔SiO₂消弱了其酸性及载体与金属粒子相互作用, 提高了Co分散和还原度及加氢活性。Hβ的微孔结构和酸性促进了初级产物裂解及异构化反应, 提高了异构烃类选择性。Co/SG/Hβ(80)催化剂较大的比表面积和微孔体积及适当的酸性中心是其高活性(CO转化率95.7%)及高航空燃油类烃选择性(42.3%, 其中异构烃为27.6%)的关键因素。

关键词: Co/SiO₂催化剂, Hβ分子筛, 费托合成, 航空燃油类烃, 孔结构

Abstract:

Bi-functional catalysts were prepared using hybrid supports, mesoporous SiO₂(SG) and microporous Hβ zeolites with different Si/Al ratios of 25, 60 and 80 for direct jet fuel-range hydrocarbon synthesis (C₈-C₁₈). The textual and structural properties of the catalysts were studied by Fourier transform infrared (FTIR), X-ray diffraction(XRD), H₂-temperature-programmed desorption(H₂-TPR) and N₂ physisorption. The results showed that catalysts supported on tailor-made SiO₂ and Hβ hybrid maintained both meso- and micro-pores with acid centers. With the decrease of Si/Al ratio, the bands corresponding to the characteristic adsorptions of Co/SG/Hβ catalysts shifted to the lower wave numbers, which accompanied by increased acidity. SiO₂ decreased the acidity of Hβ and the interaction between Co and support, resulting in high Co dispersion, reduction and CO conversion for Co/SG/Hβ. The microporous structure and acidity of Hβ accelerated the hydrocracking/hydroisomerizaion reaction, which contributed to the high selectivity to jet fuel-range isoparaffins. The increased BET surface area and microporous volume with moderate acidity of Co/SG/Hβ(80) were essential for its high CO conversion (95.7%) and selectivity to jet fuel-range hydrocarbons (42.3%, including 27.6% of isoparaffins).

Key words: Co/SiO₂ catalysts, Hβ zeolite, FT synthesis, jet fuel-range hydrocarbon, pore structure

中图分类号:

TQ426

李宇萍, 王铁军, 马隆龙, 吴创之, 定明月. Hβ改性Co/SiO₂对费托合成航空燃油类烃的影响[J]. 无机材料学报, 2014, 29(6): 599-604.

LI Yu-Ping, WANG Tie-Jun, MA Long-Long, WU Chuang-Zhi, DING Ming-Yue. Hβ Modified Co/SiO₂ Catalysts for Fischer-Tropsch Synthesis of Jet Fuel-range Hydrocarbons[J]. Journal of Inorganic Materials, 2014, 29(6): 599-604.

图/表 6

图1 Co/SG/ Hβ催化剂的XRD图谱

Fig. 1 XRD patterns of Co/SG/ Hβ catalysts

图 2 Co/SG/ Hβ催化剂的FTIR图谱

Fig. 2 FTIR spectra of Co/SG/Hβ catalysts

图3 Co/ SG/ Hβ催化剂的H2-TPR图谱

Fig. 3 H2-TPR profiles of Co/ SG/ Hβ catalysts

表1 不同催化剂的织构特征及还原分散特性

Table 1 The texture and phase properties, reducibility behavior and CO conversion of Co-based catalysts

Catalysts	S_BET/<br/>(m²·g^-1)	Micropore<br/>area/<br/>(m²·g^-1)	BJH mesopore		Micropore<br/> volume/<br/>(cm³·g^-1)	Pore size/nm		d_Co^o/<br/>nm^a	Reduction<br/>degree/<br/> %^b	Co D/<br/>%^c	X_CO/ <br/>%
Catalysts	S_BET/<br/>(m²·g^-1)	Micropore<br/>area/<br/>(m²·g^-1)	Area/<br/>(m²·g^-1)	Volume/<br/>(cm³·g^-1)	Micropore<br/> volume/<br/>(cm³·g^-1)	BJH	HK	d_Co^o/<br/>nm^a	Reduction<br/>degree/<br/> %^b	Co D/<br/>%^c	X_CO/ <br/>%
Co/SG	188	-	324	0.74	-	9.63	-	18.8	44.7	4.89	41.4
Co/SG/Hβ(25)	250	55	290	0.97	0.05	9.75	0.49	15.2	64.4	5.61	83.0
Co/SG/Hβ(60)	262	69	300	1.50	0.05	9.89	0.50	14.7	73.6	6.15	82.3
Co/SG/Hβ(80)	253	69	268	0.57	0.07	9.60	0.50	14.6	76.1	6.31	95.7
Co/Hβ(80)	425	326	-	-	0.16	-	0.50	25.2	60.7	5.23	70.6

图4 Co/SG/Hβ催化剂费托合成产物的碳数分布

Fig. 4 Carbon number distribution in FT synthesis over Co/SG/Hβ catalysts

图5 Co/SG/Hβ催化剂费托合成产物的种类分布

Fig. 5 Comparison of product species over Co/SG/Hβ catalysts (The colume from left to right: C1; C2-C7; C8-C18; C18+; CO2)

参考文献 15

[1]	LIU G, YAN B, CHEN G. Technical review on jet fuel production. Renew. Sust. Energ. Rev., 2013, 25: 59-70.
[2]	FOLKEDAHL B C, SNYDER A C, STREGE J R, et al. Process development and demonstration of coal and biomass indirect liquefaction to synthetic iso-paraffinic kerosene. Fuel Process. Technol., 2011, 92(10): 1939-1945.
[3]	MARTIN M, GROSSMANN I E. Process optimization of FT-diesel production from lignocellulosic switchgrass. Ind. Eng. Chem. Res., 2011, 50(23): 13485-13499.
[4]	KHODAKOV A Y, CHU W, FONGARLAND P. Advances in the development of novel cobalt Fischer-Tropsch catalysts for synthesis of long-chain hydrocarbons and clean fuels. Chem. Rev., 2007, 107(5): 1692-1744.
[5]	YAN Q, YU F, LIU J, et al. Catalytic conversion wood syngas to synthetic aviation turbine fuels over a multifunctional catalyst. Bioresour. Technol., 2013, 127: 281-290.
[6]	SHINODA M, ZHANG Y, YONEYAMA Y, et al. New bimodal pore catalysts for Fischer-Tropsch synthesis. Fuel Process. Technol., 2004, 86(1): 73-85.
[7]	GARDEZI S A, WOLAN J T, JOSEPH B. Effect of catalyst preparation conditions on the performance of eggshell Cobalt/SiO2 catalysts for Fischer-Tropsch synthesis. Appl. Catal. A, 2012, 447-448: 151-163.
[8]	KOMVOKIS V G, KARAKOULIA S, ILIOPOULOU E F, et al. Upgrading of Fischer-Tropsch synthesis bio-waxes via catalytic cracking: effect of acidity, porosity and metal modification of zeolitic and mesoporous aluminosilicate catalysts. Catal. Today, 2012, 196(1): 42-55.
[9]	WANG S, YIN Q, GUO J, et al. Improved Fischer-Tropsch synthesis for gasoline over Ru, Ni promoted Co/HZSM-5 catalysts. Fuel, 2013, 108: 597-603.
[10]	LI Y P, WANG T J, WU C Z, et al. Effect of Ru addition to Co/SiO2/HZSM-5 catalysts on Fischer-Tropsch synthesis of gasoline- range hydrocarbons. Catal. Commun., 2009, 10(14): 1868-1874.
[11]	TEISEH E A, CAPAREDA S, REZENOM Y H. Cobalt based hybrid Fischer-Tropsch synthesis catalyst for improved selectivity of hydrocarbons in the JP-8 carbon number range from a synthesis gas obtained from the pyrolysis of the MixAlco process derived sludge. Appl. Catal. A, 2012, 437-438: 63-71.
[12]	MARTNEZ A, ROLLAN J, ARRIBAS M A, et al. A detailed study of the activity and deactivation of zeolites in hybrid Co/SiO2-zeolite Fischer-Tropsch catalysts. J. Catal., 2007, 249(2): 162-173.
[13]	VAN STEEN E, SEWELL G S, MAKHOTHE R A, et al. TPR study on the preparation of impregnated Co/SiO2 catalysts. J. Catal., 1996, 162(2): 220-229.
[14]	LEU L J, HOU L Y, KANG B C, et al. Synthesis of zeolite beta and catalytic isomerization of n-hexane over Pt/H-beta catalysts. Appl. Catal., 1991, 69(1): 4-63.
[15]	ZHANG Y, KOIKE M, YANG R, et al. Multi-functional alumina-silica bimodal pore catalyst and its application for Fischer-Tropsch synthesis. Appl. Catal. A, 2005, 292: 252-258.

Hβ改性Co/SiO₂对费托合成航空燃油类烃的影响

Hβ Modified Co/SiO₂ Catalysts for Fischer-Tropsch Synthesis of Jet Fuel-range Hydrocarbons

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 6

参考文献 15

相关文章 15

编辑推荐

Metrics

本文评价

[1]	凌洁, 周安宁, 王文珍, 贾忻宇, 马梦丹. Cu/Mg比对Cu/Mg-MOF-74的CO₂吸附性能的影响[J]. 无机材料学报, 2023, 38(12): 1379-1386.
[2]	许伟佳, 邱大平, 刘诗强, 李敏, 杨儒. 用于高性能超级电容器电极的栓皮栎基多孔活性炭的制备[J]. 无机材料学报, 2019, 34(6): 625-632.
[3]	聂兰舰, 顾真安, 王玉芬, 向在奎, 张辰阳, 饶传东. SiO₂疏松体真空烧结致密化与透明化机理研究[J]. 无机材料学报, 2019, 34(10): 1060-1066.
[4]	孙涛, 杨琪, 喻佳瑜, 马金鑫. ZnO-C三维网络结构涂层的制备及其储锂性能研究[J]. 无机材料学报, 2017, 32(5): 483-488.
[5]	马鹏飞, 李日红, 张龙. 溶胶-凝胶法制备高比表面积铝磷钙生物活性玻璃[J]. 无机材料学报, 2017, 32(1): 107-112.
[6]	徐国忠, 金文武, 曾燮榕, 邹继兆, 熊信柏, 黄麟, 赵振宁. 煤基炭泡沫孔结构调控[J]. 无机材料学报, 2016, 31(9): 961-968.
[7]	翟丽丽, 张江, 李轩科, 丛野, 董志军, 袁观明. 模板剂F127对介孔SnO₂的孔结构及电化学性能的影响[J]. 无机材料学报, 2016, 31(6): 588-596.
[8]	易上琪, 刘洪波, 夏笑虹, 黄桂荣, 马倩, 陈玉喜. 石墨烯/炭气凝胶的制备及其结构与性能研究[J]. 无机材料学报, 2015, 30(7): 757-762.
[9]	龚云, 陈航榕, 崔香枝, 江莞, 施剑林. Pd负载型介孔ZrO₂-TiO₂复合材料的设计合成及其CO催化氧化性能研究[J]. 无机材料学报, 2013, 28(9): 992-996.
[10]	王婧, 陈颖, 朱向东, 樊渝江, 张兴栋. 双相磷酸钙陶瓷表面吸附血清蛋白的洗脱特性研究[J]. 无机材料学报, 2013, 28(10): 1143-1147.
[11]	努丽燕娜, 杨军, 郑育培, 王久林. 介孔硅酸锰镁可充镁电池正极材料的制备及其电化学性能研究[J]. 无机材料学报, 2011, 26(2): 129-133.
[12]	周颖, 王志超, 王春雷, 王六平, 许钦一, 邱介山. 大孔 - 介孔分级孔结构炭材料制备及性能研究[J]. 无机材料学报, 2011, 26(2): 145-148.
[13]	杜玉成, 颜晶, 孟琪, 李扬, 戴洪兴. Sb-SnO₂包覆硅藻土多孔导电材料制备及表征[J]. 无机材料学报, 2011, 26(10): 1031-1036.
[14]	吕岩, 王志永, 张浩, 房进, 曹高萍, 施祖进, 王碧燕. 电弧法制备石墨烯的孔结构和电化学性能研究[J]. 无机材料学报, 2010, 25(7): 725-728.
[15]	申延明, 刘丹, 吴静, 刘雅祺, 姬生菲, 李天舒. 由蜂窝状结构TBT/PMMA杂化膜制备有序孔结构的TiO₂膜[J]. 无机材料学报, 2010, 25(5): 485-489.