铈改性Silicalite-1分子筛催化剂上甲醇制丙烯反应性能研究

黄慧文; 张敏秀; 陈晨; 李春义; 崔秋凯

铈改性Silicalite-1分子筛催化剂上甲醇制丙烯反应性能研究

1.
中国石油大学(华东) 重质油国家重点实验室, 山东青岛 266580
2.
大港石化公司, 中国石油有限公司, 天津 300280

基金项目:

国家重点基础研究发展规划 973计划，2012CB215006

详细信息

中图分类号: TQ536.9
计量
- 文章访问数: 98
- HTML全文浏览量: 59
- PDF下载量: 27
- 被引次数: 0
出版历程
- 收稿日期: 2016-08-16
- 修回日期: 2016-09-20
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-12-10

Catalytic performance of cerium modified Silicalite-1 molecular sieves in the conversion of methanol to propene

1.
State Key Laboratory of Heavy Oil Processing, China University of Petroleum(East China), Qingdao 266580, China
2.
Dagang Petrochemical Company, Petro China Corporation, Tianjin 300280, China

More Information

Corresponding author: chuyli@upc.edu.cn

摘要

摘要: 采用浸渍法制备了Ce改性的Silicalite-1分子筛催化剂，利用XRD、N₂吸脱附、Py-FTIR和NH₃-TPD等手段对催化剂进行了表征；针对甲醇转化制丙烯（MTP）反应，在常压、450℃和质量空速为9.6 h^-1的反应条件下，利用连续流动固定床微型反应评价装置，考察了CeO₂负载量对CeO₂/Silicalite-1催化性能的影响。结果表明，与HZSM-5分子筛（SiO₂/Al₂O₃（molar ratio）=200）相比，Silicalite-1分子筛具有更高的丙烯选择性和催化稳定性。Ce的引入可有效调节Silicalite-1分子筛的酸性质和孔结构；合适浓度的Ce改性处理（CeO₂负载量（质量分数）为5.0%）使得Silicalite-1的强酸量降低，其丙烯选择性（质量分数）和催化稳定性分别由原来的31.9%和51 h增加到38.2%和72 h。
- 甲醇 /
- 丙烯 /
- Silicalite-1 /
- 铈 /
- 酸性
Abstract: A series of cerium modified Silicalite-1 molecular sieves were prepared by incipient wetness impregnation and used as the catalysts in the conversion of methanol to propene (MTP). The cerium modified Silicalite-1 catalysts were characterized by X-ray diffraction (XRD), N₂ sorption, pyridine adsorption Fourier transform infrared spectroscopy (Py-FTIR) and temperature-programmed desorption of NH₃ (NH₃-TPD); their catalytic performance in MTP was evaluated in a continuous flow fixed-bed micro-reactor at atmospheric pressure and 450℃, with a methanol weight hourly space velocity (WHSV) of 9.6 h^-1. The results showed that Silicalite-1 exhibits superior catalytic performance in MTP in terms of catalytic stability and selectivity to propene, in comparison with the HZSM-5 zeolite with a SiO₂/Al₂O₃ molar ratio of 200. The introduction of Ce can effectively adjust the acid properties and pore structure of Silicalite-1; modification with an appropriate concentration of Ce can reduce the amount of strong acid sites and then enhance the catalytic performance of Silicalite-1 in MTP. Over the cerium modified Silicalite-1 with a CeO₂ content of 5.0%, the selectivity to propene is increased from 31.9% to 38.2% and the catalytic lifetime is extended from 51 to 72 h, in comparison with those over the parent Silicalite-1.
- methanol /
- propene /
- Silicalite-1 /
- cerium /
- acidity

HTML全文

图 1 Silicalite-1和HZSM-5分子筛催化MTP反应评价

Figure 1 MTP over Silicalite-1 (S-1) and HZSM-5 (HZ-5) at 450℃ and atmospheric pressure with a WHSV of 9.6h^-1

methanol conversion: ■: HZ-5; ▲: S-1; propene yield: ●: HZ-5; ▼: S-1

下载: 全尺寸图片幻灯片

图 2 Silicalite-1和HZSM-5分子筛催化剂的NH₃-TPD谱图(a)和吡啶吸附红外光谱谱图(b)

Figure 2 NH₃-TPD profiles (a) and Py-FTIR spectra (b) of Silicalite-1 and HZSM-5

下载: 全尺寸图片幻灯片

图 3 HZSM-5分子筛上的硅羟基^{[24, 25]}

Figure 3 Isolated silanols (3740cm^-1) and hydrogen-bonded silanol groups (3450cm^-1) inside the chains (left) and hydrogen nests (right) of HZSM-5^{[24, 25]}

下载: 全尺寸图片幻灯片

图 4 Ce改性前后Silicalite-1分子筛催化剂的XRD谱图

Figure 4 XRD patterns of the parent and Ce-modified Silicalite-1 catalysts

a: S-1; b: 1.0Ce/S-1; c: 3.0Ce/S-1; d: 5.0Ce/S-1; e: 7.0Ce/S-1; f: 9.0Ce/S-1

下载: 全尺寸图片幻灯片

图 5 Ce改性前后Silicalite-1分子筛催化剂的Py-FTIR谱图

Figure 5 Py-FTIR spectra of the parent and Ce-modified Silicalite-1 catalysts

a: S-1; b: 1.0Ce/S-1; c: 3.0Ce/S-1; d: 5.0Ce/S-1; e: 7.0Ce/S-1; f: 9.0Ce/S-1

下载: 全尺寸图片幻灯片

图 6 Ce改性前后Silicalite-1分子筛催化剂上甲醇转化率随反应时间的变化

Figure 6 Conversion of methanol with the time on stream for MTP over the parent and Ce-modified Silicalite-1 catalysts

■: S-1; ●: 1.0Ce/S-1; ▲: 3.0Ce/S-1; ▼: 5.0Ce/S-1; ◆: 7.0Ce/S-1; □: 9.0Ce/S-1

下载: 全尺寸图片幻灯片

表 1 HZSM-5和Silicalite-1分子筛的化学组成

Table 1 Chemical composition of HZSM-5 and Silicalite-1

Sample	Elemental analysis w/%
Sample	Si	O	Al
HZ-5	46.30	53.18	0.35
S-1	46.51	53.21	0.00

下载: 导出CSV

表 2 Ce改性前后Silicalite-1分子筛催化剂的质构性质

Table 2 Textural properties of the parent and Ce-modified Silicalite-1 catalysts

Item	S-1	1.0Ce/S-1	3.0Ce/S-1	5.0Ce/S-1	7.0Ce/S-1	9.0Ce/S-1
Relative crystallinity /%	100.0	100.0	99.9	93.7	87.3	78.4
A_BET/(m²·g^-1)	394.6	384.6	372.4	370.0	329.8	326.0
A_ext/(m²·g^-1)	39.8	39.1	38.7	43.9	47.0	47.7
v_total /(cm³·g^-1)	0.23	0.22	0.21	0.21	0.19	0.19
Number of Ce /nm^-2	-	0.46	1.45	2.49	3.99	5.31

下载: 导出CSV

表 3 Ce改性前后Silicalite-1分子筛催化剂的NH₃-TPD酸性质测试

Table 3 NH₃-TPD results of the parent and Ce-modified Silicalite-1 catalysts^a

Sample	t /°C	Weak acid /(mmol·g^-1)	t /°C	Strong acid /(mmol·g^-1)	Total acid /(mmol·g^-1)	Acid density /(μmol·m^-2)
S-1	181	0.030	361	0.085	0.115	2.135
1.0Ce/S-1	183	0.033	361	0.083	0.116	2.123
3.0Ce/S-1	185	0.036	356	0.082	0.118	2.119
5.0Ce/S-1	185	0.040	354	0.080	0.120	1.824
7.0Ce/S-1	188	0.045	352	0.078	0.123	1.660
9.0Ce/S-1	189	0.061	351	0.065	0.126	1.363
^a: the calculation of acidity is based on the desorption amount of NH₃ at the corresponding temperatures

下载: 导出CSV

表 4 Ce改性前后Silicalite-1分子筛催化剂MTP反应产物选择性

Table 4 Product selectivity for MTP over the parent and Ce-modified Silicalite-1 catalysts

Sample	Selectivity s/%
Sample	CH₄	C₂H₆	C₂H₄	C₃H₈	C₃H₆	C₄H₁₀	C₄H₈	aromatics
S-1	0.4	0.0	7.0	1.0	31.9	1.7	15.9	10.7
1.0Ce/S-1	0.4	0.1	6.9	1.0	32.5	1.7	16.0	10.3
3.0Ce/S-1	0.4	0.1	6.5	0.9	34.5	1.6	18.7	9.6
5.0Ce/S-1	0.3	0.0	6.4	0.8	38.2	1.3	19.2	8.5
7.0Ce/S-1	0.4	0.0	6.7	0.9	33.9	1.6	15.5	10.1
9.0Ce/S-1	0.4	0.1	7.4	1.0	33.6	1.8	15.1	11.0

下载: 导出CSV

参考文献(33)

[1]	任诚.非石油路线制取低碳烯烃的生产技术及产业前景[J].精细化工中间体,2007,37(5):6-9. http://www.cnki.com.cn/Article/CJFDTOTAL-HNHG200705003.htm REN Chen.Production technology & industry foreground about the production of light olefins with non-oil route[J].Fine Chem Inter,2007,37(5):6-9. http://www.cnki.com.cn/Article/CJFDTOTAL-HNHG200705003.htm
[2]	ZHAO T S,TAKEMOTO T,TSUBAKI N.Direct synthesis of propylene and light olefins from dimethyl ether catalyzed by modified H-ZSM-5[J].Catal Commun,2006,7(9):647-650. doi: 10.1016/j.catcom.2005.11.009
[3]	WU W Z,GUO W Y,XIAO W D,LUO M.Dominant reaction pathway for methanol conversion to propene over high silicon H-ZSM-5[J].Chem Eng Sci,2011,66(20):4722-4732. doi: 10.1016/j.ces.2011.06.036
[4]	KOEMPEL H,LIEBNER W.Lurgi's Methanol To Propylene (MTP^®) Report on a successful commercialisation[J].Stud Surf Sci Catal,2007,167:261-267. doi: 10.1016/S0167-2991(07)80142-X
[5]	魏入朝,李春义,杨朝合,山红红.氟硅酸铵改性纳米HZSM-5分子筛的表征及催化甲醇制低碳烯烃[J].工业催化,2011,19(3):40-44. http://www.cnki.com.cn/Article/CJFDTOTAL-GYCH201103011.htm WEI Ru-chao,LI Chun-yi,YANG Chao-he,SHAN Hong-hong.Characterization and catalytic performance of (NH₄)₂SiF₆ modified nanosized HZSM-5 catalyst for conversion of methanol to olefins[J].Ind Catal,2011,19(3):40-44. http://www.cnki.com.cn/Article/CJFDTOTAL-GYCH201103011.htm
[6]	温鹏宇,梅长松,刘红星,杨为民,陈庆龄.ZSM-5硅铝比对甲醇制丙烯反应产物的影响[J].化学反应工程与工艺,2007,23(5):385-390. http://www.cnki.com.cn/Article/CJFDTOTAL-HXFY200705002.htm WEN Peng-yu,MEI Chang-song,LIU Hong-xing,YANG Wei-min,CHEN Qing-ling.Effect of Si/Al ratio in ZSM-5 on the selectivity of products for methanol conversion to propylene[J].Chem React Eng Technol,2007,23(5):385-390. http://www.cnki.com.cn/Article/CJFDTOTAL-HXFY200705002.htm
[7]	LIU J,ZHANG C X,SHEN Z H,HUA W M,TANG Y,SHEN W,YUE Y H,XU H L.Methanol to propylene:Effect of phosphorus on a high silica HZSM-5 catalyst[J].Catal Commun,2009,10(11):1506-1509. doi: 10.1016/j.catcom.2009.04.004
[8]	STOCKER M.Methanol-to-hydrocarbons:Catalytic materials and their behavior[J].Microporous Mesoporous Mater,1999,29(1):3-48. http://www.ingentaconnect.com/content/els/13871811/1999/00000029/00000001/art00319
[9]	MENG X J,YU Q J,GAO Y N,Enhanced propene/ethene selectivity for methanol conversion over pure silica zeolite:Role of hydrogen-bonded silanol groups[J].Catal Commun,2015,61:67-71. doi: 10.1016/j.catcom.2014.12.011
[10]	HEITMANN G P,DAHLHOFF G,HOLDERICH W F.Catalytically active sites for the Beckmann rearrangement of cyclohexanone oxime to ε-caprolactam[J].J Catal,1999,186(1):12-19. doi: 10.1006/jcat.1999.2552
[11]	BONELLI B,FOMI L,ALOISEl A,NAGY J B,FOMASARI G,GARRONE E,GEDEON A,GIORDANO G,TRIFIRO F.Beckmann rearrangement reaction:About the role of defect groups in high silica zeolite catalysts[J].Microporous Mesoporous Mater,2007,101(1):153-160. http://www.doc88.com/p-9025335182516.html
[12]	FLEGO C,DALLORO L.Beckmann rearrangement of cyclohexanone oxime over silicalite-1:An FT-IR spectroscopic study[J].Microporous Mesoporous Mater,2003,60(1):263-271.
[13]	THIBAULT-STARZYK F,VIMORIT A,GILSON J P.2D-COS IR study of coking in xylene isomerisation on H-MFI zeolite[J].Catal Today,2001,70(1):227-241. https://www.researchgate.net/publication/209129401_2D-COS_IR_study_of_coking_in_xylene_isomerisation_on_H-MFI_zeolite
[14]	ARUDRA P,BHUIYAN T I,AKHTARR M N,AITANI A M,AL-KHATTAF S S,HATTORI H.Silicalite-1 as efficient catalyst for production of propene from 1-butene[J].ACS Catal,2014,4(11):4205-4214. doi: 10.1021/cs5009255
[15]	MEI C S,WEN P Y,LIU Z C,LIU H X,WANG Y D,YANG W M,XIE Z K,HUA W M,GAO Z.Selective production of propylene from methanol:Mesoporosity development in high silica HZSM-5[J].J Catal,2008,258(1):243-249. doi: 10.1016/j.jcat.2008.06.019
[16]	姜坤,严丽霞,虞贤波,王靖岱,阳永荣.磷修饰高硅ZSM-5球形催化剂的甲醇制丙烯反应性能[J].北京理工大学学报,2011,31(10):1247-1251. http://www.cnki.com.cn/Article/CJFDTOTAL-BJLG201110023.htm JING Kun,YAN Li-xia,YU Xin-bo,WANG Jing-dai,YANG Yong-rong.Phosphorous modifiedhigh silica ZSM-5 spherical catalyst and its reaction on methanol to propene[J].J Beijing Ins Technol (Chin Ed),2011,31(10):1247-1251. http://www.cnki.com.cn/Article/CJFDTOTAL-BJLG201110023.htm
[17]	胡思,张卿,夏至,巩雁军,徐君,邓风,窦涛.氟硅酸铵改性纳米HZSM-5分子筛催化甲醇制丙烯[J].物理化学学报,2012,28(11):2705-2712. http://www.cnki.com.cn/Article/CJFDTOTAL-WLHX201211027.htm HU Si,ZHANG Qing,XIA Zhi,GONG Yan-jun,XU Jun,DENG Feng,DOU Tao.Catalytic conversion of methanol to propylene over (NH₄)₂SiF₆-modified nanosized HZSM-5 zeolite[J].Acta Phys Chim Sin,2012,28(11):2705-2712. http://www.cnki.com.cn/Article/CJFDTOTAL-WLHX201211027.htm
[18]	毛东森,郭强胜,孟涛,卢冠忠.水热处理对纳米HZSM-5分子筛酸性及催化甲醇制丙烯反应性能的影响[J].物理化学学报,2010,26(2):338-344. http://www.cnki.com.cn/Article/CJFDTOTAL-WLHX201002015.htm MAO Dong-sen,GUO Sheng-qiang,MEN Tao,LU Guan-zhong.Effect of hydrothermal treatment on the acidity and catalytic performance of nanosized HZSM-5 zeolites for the conversion of methanol to propene[J].Acta Phys Chim Sin,2010,26(2):338-344. http://www.cnki.com.cn/Article/CJFDTOTAL-WLHX201002015.htm
[19]	SUN C,DU J M,LIU J,YANG Y S,REN N,SHEN W,XU H L,TANG Y.A facile route to synthesize endurable mesopore containing ZSM-5 catalyst for methanol to propylene reaction[J].Chem Commun,2010,46(15):2671-2673. doi: 10.1039/b925850g
[20]	KIM J,CHOI M,RYOO R.Effect of mesoporosity against the deactivation of MFI zeolite catalyst during the methanol-to-hydrocarbon conversion process[J].J Catal,2010,269(1):219-228. doi: 10.1016/j.jcat.2009.11.009
[21]	赵国良,滕加伟,谢在库,唐颐,杨为明,陈庆龄.氟硅酸铵改性的HZSM-5催化剂的表征及其碳四烯烃裂解催化性能[J].催化学报,2005,26(12):1083-1087. http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA200512010.htm ZHAO Guo-liang,TENG Jia-wei,XIE Zai-ku,TANG Yi,YANG Wei-min,CHEN Qing-ling.Characterization and catalytic performance of (NH₄)₂SiF₆-modified HZSM-5 catalyst for C₄olefin cracking[J].Chin J Catal,2005,26(12):1083-1087. http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA200512010.htm
[22]	吴伟,吴维果,李凌飞,杨巍,武光.氟硅酸铵改性的HZSM-12分子筛催化合成2,6-二甲基萘[J].石油学报(石油加工),2010,26(2):189-194. http://www.cnki.com.cn/Article/CJFDTOTAL-SXJG201002007.htm WU Wei,WU Wei-guo,LI Lin-fei,YANG Wei,WU Guang.Shape-selective synthesis of 2,6-dimethylnaphtalene (NH₄)₂SiF₆-modified HZSM-12 zeolite[J].Acta Pet Sin (Pet Process Sect),2010,26(2):189-194. http://www.cnki.com.cn/Article/CJFDTOTAL-SXJG201002007.htm
[23]	BARBERA K,BONINO F,BORDIGA S,JANSSENS T V W,BEATO P,Structure-deactivation relationship for ZSM-5 catalysts governed by framework defects[J].J Catal,2011,280(2):196-205. doi: 10.1016/j.jcat.2011.03.016
[24]	BORDIGA S,UGLIENGO P,DAMIN A,LAMBERITA C,SPOTO G,ZECCHINA A,SPANO G,BUZZONI R,DALLORO L,RIVETTI F.Hydroxyls nests in defective silicalites and strained structures derived upon dehydroxylation:Vibrational properties and theoretical modelling[J].Top Catal,2001,15(1):43-52. doi: 10.1023/A:1009019829376
[25]	BOLIS V,BUSCO C,BORDIGA S,UGLIENGO P,LAMBERTI C,ZECCHINA A.Calorimetric and IR spectroscopic study of the interaction of NH₃ with variously prepared defective silicalites:Comparison with ab initio computational data[J].Appl Surf Sci,2002,196(1):56-70. https://www.researchgate.net/publication/229339123_Calorimetric_and_IR_spectroscopic_study_of_the_interaction_of_NH_3_with_variously_prepared_defective_silicalites-Comparison_with_ab_initio_computational_data_Appl_Surf_Sci_1961-4_56-70
[26]	GABRIENKO AA,DANILOVA I G,ARZUMANOY S S,TOKTAREV A V,FREUDE D,STEPANOV A G.Strong acidity of silanol groups of zeolite beta:Evidence from the studies by IR spectroscopy of adsorbed CO and ¹H MAS NMR[J].Microporous Mesoporous Mater,2010,131(1):210-216.
[27]	PARK J W,KIM S J,SEO M,KIM S Y,SUGI Y,SEO G.Product selectivity and catalytic deactivation of MOR zeolites with different acid site densities in methanol-to-olefin (MTO) reactions[J].Appl Catal A:Gen,2008,349(1/2):76-85. https://www.researchgate.net/publication/244109004_Product_selectivity_and_catalytic_deactivation_of_MOR_zeolites_with_different_acid_site_densities_in_methanol-to-olefin_MTO
[28]	桂建舟,张晓彤,胡之德,孙兆林.正己烷在ZnNi/HZSM-5上芳构化反应的研究[J].兰州大学学报:自然科学版,2003,39(5):61-65. http://www.cnki.com.cn/Article/CJFDTOTAL-LDZK200305014.htm GUI Jian-zhou,ZHANG Xiao-tong,HU Zhi-de,SUN Zhao-lin.A study of n-hexane aromatization on the ZnNi/HZSM-5 catalyst[J].J Univ Lanzhou (Nat Sci),2003,39(5):61-65. http://www.cnki.com.cn/Article/CJFDTOTAL-LDZK200305014.htm
[29]	OTHMAN I,MOHAMED R M,IBRAHIM I A,MOHAMED M M.Synthesis and modification of ZSM-5 with manganese and lanthanum and their effects on decolorization of indigo carmine dye[J].Appl Catal A:Gen,2006,299:95-102. doi: 10.1016/j.apcata.2005.10.016
[30]	ITOH H,HIDALGO C V,HATTORI T,NIWA M,MURAKAMI Y.Role of acid property of various zeolites in the methanol conversion to hydrocarbons[J].J Catal,1984,85(2):521-526. doi: 10.1016/0021-9517(84)90241-0
[31]	GAYUBO A G,BENITO P L,AGUAYO A T,OLAZAR M,BILBAO J.Relationship between surface acidity and activity of catalysts in the transformation of methanol into hydrocarbons[J].J Chem Technol Biotechnol,1996,65(2):186-192. doi: 10.1002/(ISSN)1097-4660
[32]	SVELLE S,JOENSEN F,NERLOV J,OLSBYE U,LILLERUD K P,KOLBOE S,BJORGEN M.Conversion of methanol into hydrocarbons over zeolite H-ZSM-5:Ethene formation is mechanistically separated from the formation of higher alkenes[J].J Am Chem Soc,2006,128(46):14770-14771. doi: 10.1021/ja065810a
[33]	BJØRGEN M,SVELLE S,JOENSEN F,NERLOV J,KOLBOE S,BONINO F,PALUMBO L,BORDIGA S,OLSBYE U.Conversion of methanol to hydrocarbons over zeolite H-ZSM-5:On the origin of the olefinic species[J].J Catal,2007,249(2):195-207. doi: 10.1016/j.jcat.2007.04.006