无定形硅铝催化生物质热裂解气齐聚合成汽油的特性

doi:10.7503/cjcu20160309

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (11): 2060.doi: 10.7503/cjcu20160309

无定形硅铝催化生物质热裂解气齐聚合成汽油的特性

张浅^1,², 定明月¹(), 张玉兰^1,², 李宇萍¹, 王晨光¹, 王铁军¹(), 马隆龙¹

1. 中国科学院可再生能源重点实验室, 中国科学院广州能源研究所, 广东省新能源和可再生能源研究开发与应用重点实验室, 广州 510640
2. 中国科学院大学, 北京 100049

收稿日期:2016-05-05 出版日期:2016-11-10 发布日期:2016-10-17
作者简介:联系人简介: 王铁军, 男, 博士, 研究员, 博士生导师, 主要从事煤及生物质直接和间接液化合成液体燃料技术的研究. E-mail: wangtj@ms.giec.ac.cn; 定明月, 男, 研究员, 主要从事生物质液体燃料合成方面的研究. E-mail: dingmy@ms.giec.ac.cn
基金资助:
国家自然科学基金(批准号: 51561145010, U1362109)、国家“九七三”计划项目(批准号: 2013CB228105)和广东省科技计划项目(批准号: 2013B010405012, 2015A010106011, 2016A050502037)资助

Oligomerization of Biomass Cracking Gas to Gasoline Distillates over Amorphous Silica-alumina^†

ZHANG Qian^1,², DING Mingyue^1,^*(), ZHANG Yulan^1,², LI Yuping¹, WANG Chenguang¹, WANG Tiejun^1,^*(), MA Longlong¹

1. Key Laboratory of Renewable Energy, Chinese Academy of Sciences, Guangzhou Institute of Energy Conversion,Chinese Academy of Sciences, Guangdong Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, China
2. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2016-05-05 Online:2016-11-10 Published:2016-10-17
Contact: DING Mingyue,WANG Tiejun E-mail:dingmy@ms.giec.ac.cn;wangtj@ms.giec.ac.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.51561145010, U1362109), the National Key Basic Research Program of China(No.2013CB228105) and the Science and Technology Planning Project of Guangdong Province, China(Nos.2013B010405012, 2015A010106011, 2016A050502037)

摘要/Abstract

摘要：

选取无定形硅铝(ASA)作为生物质热裂解气齐聚反应催化剂, 分析了齐聚反应前后ASA的织构性质、酸性和积碳行为的变化规律, 并在固定床反应器中评价了ASA在不同反应条件(100~320 ℃, 2.0~4.0 MPa)下的齐聚反应性能. 结果表明, 在不同齐聚反应条件下ASA均有不同程度的酸性损失和积碳, L酸位量损失随着温度升高呈现先降低后增加的趋势, 在280 ℃达到最低; 压力的升高则有利于降低L酸位量的损失. 催化剂积碳量变化与L酸位量变化趋势一致. 在反应过程中, 低碳烯烃转化率和汽油段产物收率随着温度和压力的升高逐渐增大, 在4.0 MPa, 280 ℃反应条件下达到最优, 其乙烯、丙烯和丁烯的反应转化率分别为19.2%, 37.3%和58.7%, 汽油段产物收率(摩尔分数)为22.9%, $C 5 +$ 的烯烃类选择性可达73.5%.

关键词: 生物质热解气, 富低碳烯烃, 烯烃齐聚, 无定形硅铝, 固定床

Abstract:

The oligomerization performances of biomass cracking gas over amorphous silica-alumina(ASA) were investigated in a fixed bed in the region of 100—320 ℃ and 2.0—4.0 MPa. NH₃-TPD, Py-IR, TG, SEM, BET and XRD were used to characterize the surface structures, acidity properties and carbon deposition of catalysts. The results showed that there were different degrees of acid amount loss and carbon deposition for ASA during oligomerization under different reaction conditions. The loss of Lewis acid amount decreased gra-dually with increasing temperature, and reached the minimum at 280 ℃, and then begun to increase with continual increase of temperature. The increase of pressure is beneficial to reduce the Lewis acid loss. The change trend of carbon deposition was consistent with that of Lewis acid loss. During oligomerization, the conversion of light olefins and yield of gasoline range products increased gradually with the increase of temperature and pressure, and reached the maximum at 4.0 MPa and 280 ℃. The conversions of ethylene, propylene and butylene reached 19.2%, 37.3% and 58.7%, respectively. The yield of gasoline range product reached 22.9%(molar fraction), and the selectivity of C⁵⁺olefins reached 73.5%.

Key words: Biomass cracking gas, Riched light olefin, Olefins oligomerization, Amorphous silica-alumina, Fixed-bed reactor

中图分类号:

O643

TrendMD:

张浅, 定明月, 张玉兰, 李宇萍, 王晨光, 王铁军, 马隆龙. 无定形硅铝催化生物质热裂解气齐聚合成汽油的特性. 高等学校化学学报, 2016, 37(11): 2060.

ZHANG Qian, DING Mingyue, ZHANG Yulan, LI Yuping, WANG Chenguang, WANG Tiejun, MA Longlong. Oligomerization of Biomass Cracking Gas to Gasoline Distillates over Amorphous Silica-alumina^†. Chem. J. Chinese Universities, 2016, 37(11): 2060.

图/表 15

Fig.1 Schematic diagram of the catalytic reactor system for the oligomerization of olefin-rich biomass syngas

Table 1 Reaction conditions for ASA catalysis oligomerization of olefin-rich biomass syngas*

Run No.	t/℃	p/MPa
R1	100	4.0
R2	200	4.0
R3	240	4.0
R4	280	4.0
R5	320	4.0
R6	280	2.0
R7	280	3.0

Fig.2 SEM images of the ASA with different magnifications

Table 2 Physical and chemical characteristics of ASA before and after different reactions

Catalyst	S_BET/ (m²·g^-1)	Average pore diameter/nm	Pore volume/ (cm³·g^-1)
ASA(Fresh)	467.2	4.33	0.73
ASA-R1	279.9	4.31	0.37
ASA-R2	330.8	3.83	0.43
ASA-R3	307.4	3.81	0.44
ASA-R4	320.9	4.32	0.49
ASA-R5	249.1	3.81	0.35
ASA-R6	361.1	4.29	0.55
ASA-R7	335.1	4.32	0.52

Fig.3 XRD patterns of ASA before and after different reactionsa. ASA-fresh; b. ASA-R1; c. ASA-R2; d. ASA-R3;e. ASA-R4; f. ASA-R5; g. ASA-R6; h. ASA-R7.

Fig.4 NH3-TPD profiles of the ASA catalyst

Table 3 NH3-TPD data of ASA catalyst

Sample	Acid amount/(μmol·g^-1)			T-peak/℃
Sample	Weak acid	Strong acid	Total acid	LT-peak	HT-peak
ASA	77.29	530.34	607.63	230	500

Fig.5 IR spectra of ASA under different conditions a. ASA-fresh; b. ASA-R1; c. ASA-R2; d. ASA-R3; e. ASA-R4; f. ASA-R5; g. ASA-R6; h. ASA-R7.

Table 4 Py-IR data of ASA catalyst

Catalyst	Content of Brönsted acid/ (mmol·g^-1)	Content of Lewis acid/ (mmol·g^-1)	Catalyst	Content of Brönsted acid/ (mmol·g^-1)	Content of Lewis acid/ (mmol·g^-1)
ASA-fresh	0.0304	0.1047	ASA-R4	0.0168	0.0536
ASA-R1	0.0212	0.0612	ASA-R5	0.0244	0.0345
ASA-R2	0.0156	0.0429	ASA-R6	0.0227	0.0478
ASA-R3	0.0199	0.0510	ASA-R7	0.0234	0.0418

Fig.6 TG(A) and DTG(B) analysis curves of catalyst deposited with carbona. ASA-fresh; b. ASA-R1; c. ASA-R2; d. ASA-R3; e. ASA-R4; f. ASA-R5; g. ASA-R6; h. ASA-R7.

Fig.7 TG coke mass loss ratio(histogram) and the loss of mesopore volume ratio(●), loss of Lewis acid site ratio(▲) in different reaction conditions

Fig.8 Carbon conversion of olefin oligomerization under different reaction conditions a. C2H4; b. C3H6; c. C4H8. (A) 4.0 MPa, 100—320 ℃; (B) 2.0—4.0 MPa, 280 ℃.

Fig.9 Effects of reaction temperature on space-time yield(A) and product distribution(B) of olefin oligomerization with 4.0 MPa

Run No.	Carbon yield of liquid(%)	Product distribution(%, mass fraction)
Run No.	Carbon yield of liquid(%)	C₅	C₆	C₇	C₈	C₉	C₁₀	$C 11 +$
R1	2.14	1.30	0.99	39.81	1.08	1.27	51.56	3.99
R2	7.94	5.03	8.61	47.99	7.96	4.09	22.20	4.12
R3	17.56	5.07	13.89	49.92	12.33	4.71	12.23	1.86
R4	22.91	4.21	16.17	56.12	13.46	1.41	6.80	1.83
R5	20.16	5.73	18.65	55.61	8.61	4.46	4.47	2.17

Run No.	Carbon yield of liquid(%)	Product distribution(%, mass fraction)
Run No.	Carbon yield of liquid(%)	C₅	C₆	C₇	C₈	C₉	C₁₀	$C 11 +$
R1	2.14	1.30	0.99	39.81	1.08	1.27	51.56	3.99
R2	7.94	5.03	8.61	47.99	7.96	4.09	22.20	4.12
R3	17.56	5.07	13.89	49.92	12.33	4.71	12.23	1.86
R4	22.91	4.21	16.17	56.12	13.46	1.41	6.80	1.83
R5	20.16	5.73	18.65	55.61	8.61	4.46	4.47	2.17

参考文献 27

[1]	Tomov A., K. , Gibson V., C. , Britovsek G. J., P. , Long R., J. , Meurs M., V. , Jones D., J. , Organometallics, 2009, 28( 24), 7033- 7040
[2]	王俊, 杨光, 李翠勤, 施伟光. 高等学校化学学报, 2014, 35( 7), 1536- 1540
	Wang, J. , Yang, G. , Li C., Q. , Shi W., G. , Chem. J. Chinese Universities, 2014, 35( 7), 1536- 1540 (
[3]	Corma, A. , Melo, F.V. , Sauvanaud, L. , Ortega, F. , Catal. Today, 2005, 107, 699- 706
[4]	Park Y., K. , Lee C., W. , Kang N., Y. , Choi W., C. , Choi, S. , Oh S., H. , Park D., S. , Catal. Surv. Asia, 2010, 14, 75- 84
[5]	纪华, 吕毅军, 胡津仙, 相宏伟, 李永旺. 化学进展, 2002, 14( 2), 146- 155
	Ji, H. , Lü, Y. J. , Hu J., X. , Xiang H., W. , Li Y., W. , Progress in Chemistry, 2002, 14( 2), 146- 155 (
[6]	王俊, 霍宏亮, 李翠勤, 马立莉, 施伟光, 陈帅. 高等学校化学学报, 2015, 36( 9), 1813- 1818
	Wang, J. , Huo H., L. , Li C., Q. , Ma L., L. , Shi W., G. , Chen, S. , Chem. J. Chinese Universities, 2015, 36( 9), 1813- 1818 (
[7]	Zhang, H. , Cheng Y., T. , Vispute T., P. , Xiao, R. , Huber G., W. , Energy Environ Sci., 2011, 4, 2297- 2307
[8]	Gayubo A., G. , Valle, B. , Aguayo A., T. , Olazar, M. , Bilbao, J. , Industrial & Engineering Chemistry Research, 2009, 49( 1), 123- 131
[9]	Bjorgen, M. , Svelle, S. , Joensen, F. , Nerlov, J. , Kolboe, S. , Bonino, F. , Palumbo, L. , Bordiga, S. , Olsbye, U. , J. Catal., 2007, 249, 195- 207
[10]	Bradin, D. , Production of Polypropylene from Renewable, Resources , WO, US8916661, 2014
[11]	Antonio, M. , Polymer Reviews, 2009, 49( 2), 79- 84
[12]	Qi, Y. , Liu, Z. , Lv, Z. , Wang, H. , He, C. , Xu, L. , A Process for Producing Lower Carbon Olefins from Methanol or/and Dimethyl, Ether , EP, WO 2008106841 A8, 2009
[13]	Yang G., H. , Tsubaki, N. , Shamoto, J. , Yoneyama, Y. , Zhang, Y. , J. Am. Chem. Soc., 2010, 132, 8129- 8136
[14]	Corma, A. , Iborra, S. , Velty, A. , Chem. Rev., 2007, 107, 2411- 2502
[15]	Cheng, J. , Hu, P. , Ellis, P. , French, S. , Kelly, G. , Lok C., M. , J. Catal., 2008, 257, 221- 228
[16]	George, W. , Huber, P. , Corma, A. , Angew. Chem., 2007, 46( 38), 7184- 7201
[17]	Vispute T., P. , Zhang, H. , Sanna, A. , Xiao, R. , Huber G., W. , Science, 2010, 330( 6008), 1222- 1227
[18]	Gong, F. , Yang, Z. , Hong, C. , Huang, W. , Shen, N. , Zhang, Z. , Bioresource Technology, 2011, 102( 19), 9247- 9254
[19]	Yuan, Y. , Bi, P. , Fan, M. , Zhang, Z. , Jiang, P. , Li, Q. , Journal of Chemical Technology & Biotechnology, 2014, 89( 2), 239- 248
[20]	de Klerk, A. , Energy & Fuels, 2006, 20, 1799- 1805
[21]	Lin, S. , Shi, L. , Zhang, H. , Zhang, N. , Yi, X. , Zheng, A. , Microporous & Mesoporous Materials, 2014, 184( 2), 151- 161
[22]	Bleken F., L. , Barbera, K. , Bonino, F. , Olsbye, U. , Lillerud K., P. , Bordiga, S. , Journal of Catalysis, 2013, 307( 6), 62- 73
[23]	谭伟, 侯珂珂, 刘民, 李文慧, 刘海鸥, 宋春山, 郭新闻. 石油学报, 2002, 21( 7), 955- 957
	Tan, W. , Hou K., K. , Liu, M. , Li W., H. , Liu H., O. , Song C., S. , Guo X., W. , Acta Petrolei Sinica, 2002, 21( 7), 955- 957 (
[24]	Helveg, S. , Lopez, C. , Schested, J. , Nature, 2004, 427, 426- 429
[25]	Martí, nez C. , Doskocil E., J. , Corma, A. , Topics in Catalysis, 2013, 57( 6-9), 668- 682
[26]	胡津仙, 李晓波, 李英, 王锋, 任杰, 李永旺. 分子催化, 2005, 19( 1), 17- 21
	Hu J., X. , Li X., B. , Li, Y. , Wang, F. , Ren, J. , Li Y., W. , J. Mol. Catal., 2005, 19( 1), 17- 21 (
[27]	Bjorgen, M. , Olsbye, U. , Kolboe, S. , Journal of Catalysis, 2003, 215( 1), 30- 44

无定形硅铝催化生物质热裂解气齐聚合成汽油的特性

Oligomerization of Biomass Cracking Gas to Gasoline Distillates over Amorphous Silica-alumina^†

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无定形硅铝催化生物质热裂解气齐聚合成汽油的特性

Oligomerization of Biomass Cracking Gas to Gasoline Distillates over Amorphous Silica-alumina†

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Oligomerization of Biomass Cracking Gas to Gasoline Distillates over Amorphous Silica-alumina^†