H<i>β</i>/Al-SBA-15介微孔复合分子筛负载Ni-W催化剂对萘加氢裂化制BTX的催化性能

程俊杰; 李振荣; 赵亮富

Hβ/Al-SBA-15介微孔复合分子筛负载Ni-W催化剂对萘加氢裂化制BTX的催化性能

程俊杰^{1, 2},
李振荣¹,
赵亮富^1, ,

1.
中国科学院山西煤炭化学研究所应用催化与绿色化工实验室, 山西太原 030001
2.
中国科学院大学, 北京 100049

基金项目:

中国科学院战略性先导科技专项 XDA07020200

中国科学院战略性先导科技专项 XDA07020400

详细信息

通讯作者:
赵亮富, Tel:0351-6018564, 0351-4041526, E-mail:lfzhao@sxicc.ac.cn

中图分类号: O643
计量
- 文章访问数: 133
- HTML全文浏览量: 60
- PDF下载量: 10
- 被引次数: 0
出版历程
- 收稿日期: 2016-09-30
- 修回日期: 2016-11-25
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-01-10

Catalytic performance of Ni-W supported on micro-mesoporous Hβ/Al-SBA-15 composite molecular sieves in the hydrocracking of naphthalene to BTX

1.
Laboratory of Applied Catalysis and Green Chemical Engineering, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Funds:

Strategic Leading Science and Technology of Chinese Academy of Sciences XDA07020200

and Leading Science and Technology of Chinese Academy of Sciences XDA07020400

摘要

摘要: 采用后合成法制备Hβ/Al-SBA-15复合分子筛，利用XRD、N₂吸附、Py-IR、NH₃-TPD、SEM和TEM等手段进行表征。用浸渍法将Ni-W活性组分担载在Hβ/Al-SBA-15载体上，制备Ni-W/Hβ/Al-SBA-15催化剂，以萘为模型化合物，考察该催化剂的加氢裂化性能。结果表明，所合成的Hβ/Al-SBA-15复合分子筛既有介孔结构又有微孔结构，并同时具有B酸和L酸中心，酸性强于SBA-15。具有适度酸性位和介微孔结构的Ni-W/Hβ/Al-SBA-15催化剂，对萘加氢裂化具有较高的萘转化率和BTX选择性，分别为96%和61.1%。
- 介微孔材料 /
- 萘 /
- 加氢裂化 /
- BTX /
- Hβ/Al-SBA-15复合分子筛 /
- Ni-W
Abstract: Micro-mesoporous Hβ/Al-SBA-15 composite molecular sieves was prepared by post-synthesis method and characterized by XRD, N₂ sorption, Py-FTIR, NH₃-TPD, SEM and TEM. With the Hβ/Al-SBA-15 composite as support, Ni-W/Hβ/Al-SBA-15 catalyst was prepared through impregnation and its catalytic performance in the hydrocracking of naphthalene to BTX was investigated. The results verified that the Hβ/Al-SBA-15 composite are provided with both micropores and mesopores. Both Bronsted acid and Lewis acid sites are present on the surface of Hβ/Al-SBA-15 and its acidity is stronger than that of SBA-15. After loading Ni and W, the Ni-W/Hβ/Al-SBA-15 catalyst with moderate acidity and micro-mesoporous structure exhibits high activity in the hydrocracking of naphthalene to BTX; the conversion of naphthalene reaches 96%, with the selectivity of 61.1% to BTX.
- micro-mesopore material /
- naphthalene /
- hydrocraking catalyst /
- BTX /
- Hβ/Al-SBA-15 composite /
- Ni-W

HTML全文

图 1 分子筛的XRD谱图

Figure 1 XRD patterns of the composite molecular sieve

(a): at small angle; (b): at large angle
a: Hβ/Al-SBA-15; b: Al-SBA-15; c: SBA-15; d: Hβ

下载: 全尺寸图片幻灯片

图 2 复合分子筛的N₂吸附-脱附等温线

Figure 2 N₂ adsorption-desorption isotherms of the composite molecular sieve

a: SBA-15; b: Al-SBA-15; c: Hβ/Al-SBA-15; d: Hβ

下载: 全尺寸图片幻灯片

图 3 各种分子筛样品的Py-FTIR谱图

Figure 3 Py-FTIR spectra of different molecular sieves

a: Hβ; b: Al-SBA-15; c: SBA-15; d: Hβ/Al-SBA-15

下载: 全尺寸图片幻灯片

图 4 各种分子筛样品的NH₃-TPD谱图

Figure 4 NH₃-TPD profiles of various molecular sieves

a: SBA-15; b: Hβ/Al-SBA-15; c: Hβ

下载: 全尺寸图片幻灯片

图 5 各种分子筛样品的SEM照片

Figure 5 SEM images of various molecular sieves

(a): SBA-15; (b): Hβ/Al-SBA-15; (c): Hβ

下载: 全尺寸图片幻灯片

图 6 各种分子筛样品TEM照片

Figure 6 TEM images of various molecular sieves

(a): SBA-15; (b): Hβ; (c): Hβ/Al-SBA-15

下载: 全尺寸图片幻灯片

图 7 反应温度对转化率及选择性的影响

Figure 7 Influences of reaction temperature on the conversion and selectivity

■: naphthalene conversion; ●: selectivity to BTX

下载: 全尺寸图片幻灯片

图 8 氢油比对转化率及选择性的影响

Figure 8 Influences of hydrogen-oil volume ratio on the conversion and selectivity

■: naphthalene conversion; ●: selectivity to BTX

下载: 全尺寸图片幻灯片

图 9 反应压力对转化率及选择性的影响

Figure 9 Influences of reaction pressure on the conversion and selectivity

■: naphthalene conversion; ●: selectivity to BTX

下载: 全尺寸图片幻灯片

图 10 空速对转化率及选择性的影响

Figure 10 Influences of WHSV on the conversion and selectivity

■: naphthalene conversion; ●: selectivity to BTX

下载: 全尺寸图片幻灯片

图 11 加氢裂化产物中BTX分布

Figure 11 Distribution of BTX in the products of naphthalene hydrocracking

下载: 全尺寸图片幻灯片

表 1 不同分子筛的孔结构性质

Table 1 Textural properties of different molecular sieves

Sample	A_BET /(m²·g^-1)	v_BJH /(cm³·g^-1)	d_AEVR /nm
SBA-15	696.48	1.12	6.41
Al-SBA-15	755.19	1.12	5.92
Hβ/Al-SBA-15	669.84	0.93	6.48
Hβ	487.02	0.42	0.93

下载: 导出CSV

表 2 分子筛的酸性

Table 2 Acidity of various molecular sieves

Sample	B acid sites /(μmol·g^-1)		L acid sites /(μmol·g^-1)		B/L
Sample	200 ℃	450 ℃	200 ℃	450 ℃	200 ℃	450 ℃
Hβ	113.84	3.06	256.76	30.22	0.44	0.10
Al-SBA-15	2.85	0.25	5.78	1.75	0.49	0.14
SBA-15	0.80	0.34	15.71	11.43	0.05	0.03
Hβ/Al-SBA-15	17.20	0.93	28.59	18.89	0.60	0.05

下载: 导出CSV

参考文献(15)

[1]	DONG W L, JAE Y J, TAE W K, SANG E S, SUNG H B. Selective hydrodealkylation of C₉⁺ aromatics to benzene, toluene and xylenes (BTX) over a Pt/H-ZSM-5 catalyst[J]. J Mol Catal A:Chem, 2015, 407:147-151. doi: 10.1016/j.molcata.2015.06.035
[2]	ELFADLY A, ZEID I, YEHIA F, RABIE A, ABOUALALA M, PARK S. Highly selective BTX from catalytic fast pyrolysis of lignin over supported mesoporous silica[J]. Int J Biol Macromol, 2016, 91:278-93. doi: 10.1016/j.ijbiomac.2016.05.053
[3]	SULTANA A, FUJITANI T. Conversion of levulinic acid to BTX over different zeolite catalysts[J]. Catal Commun, 2017, 88:26-29. doi: 10.1016/j.catcom.2016.09.023
[4]	诸荣, 陈航榕, 施剑林, 严东生.以嵌段共聚物为结构导向剂的SBA-15和SBA-16的合成及表征[J].无机材料学报, 2003, 18(4):855-860. http://www.cnki.com.cn/Article/CJFDTOTAL-WGCL200304023.htm ZHU Rong, CHEN Hang-rong, SHI Jian-lin, YAN Dong-sheng. Synthesis and characterization of SBA-15 and SBA-16 templated by block copolymers[J]. J Inorg Mater, 2003, 18(4):855-860. http://www.cnki.com.cn/Article/CJFDTOTAL-WGCL200304023.htm
[5]	许峰, 顾建峰, 关乃佳, 袁忠勇. Mg改性ZSM-5/AlPO₄-5复合分子筛用于甲苯甲醇侧链烷基化反应[J].石油学报(石油加工), 2008, 346(4):346-349. http://www.cqvip.com/qk/94167X/2008B10/28596429.html XU Feng, GU Jian-feng, GUAN Nai-jia, YUAN Zhong-yong. Magnesium modified ZSM-5/AlPO₄-5 composite zeolite for side-chain alkylation of toluene with methanol[J]. Acta Pet Sin (Pet Process Sect), 2008, 346(4):346-349. http://www.cqvip.com/qk/94167X/2008B10/28596429.html
[6]	徐新龙, 沈健.复合分子筛β/SBA-15的合成及表征[J].精细化工, 2014, 31(5):591-596. http://www.cnki.com.cn/Article/CJFDTOTAL-JXHG201405010.htm XU Xin-long, SHEN Jian. Synthesis and characterization of composite molecular sieves Beta/SBA-15[J]. Fine Chem, 2014, 31(5):591-596. http://www.cnki.com.cn/Article/CJFDTOTAL-JXHG201405010.htm
[7]	李猛, 傅吉全.用ZSM-5降解液进行SBA-15分子筛合成的研究[J].北京化工大学学报(自然科学版), 2010, 37(4):88-93. http://www.cnki.com.cn/Article/CJFDTOTAL-BJHY201004018.htm LI Meng, FU Ji-quan. Synthesis of SBA-15 by using the dissolution of ZSM-5 zeolite[J]. J Beijing Univ Chem Technol (Nat Sci Ed), 2010, 37(4):88-93. http://www.cnki.com.cn/Article/CJFDTOTAL-BJHY201004018.htm
[8]	CORMA A. From microporous to mesoporous molecular sieve materials and their use in catalysis[J]. Chem Rev, 1997, 97(6):2373-2419. doi: 10.1021/cr960406n
[9]	王洪平, 张泽凯, 陈银飞.高硅β分子筛的原位合成及其在甲苯催化燃烧中的应用[J].石油化工, 2011, 40(11):1158-1164. http://www.cnki.com.cn/Article/CJFDTOTAL-SYHG201111005.htm WANG Hong-ping, ZHANG Ze-kai, CHEN Yin-fei. In situ synthesis of high-silica β zeolite over cordierite support and its application in catalytic combustion of toluene[J]. Petrkchem Technol, 2011, 40(11):1158-1164. http://www.cnki.com.cn/Article/CJFDTOTAL-SYHG201111005.htm
[10]	VU X H, URSULA B, MICHAEL H. Direct synthesis of nanosized-ZSM-5/SBA-15 analog composites from preformed ZSM-5 precursors for improved catalytic performance as cracking catalyst[J]. J Mater Sci, 2014, 49(16):5676-5689. doi: 10.1007/s10853-014-8287-z
[11]	徐新龙, 沈健. β/SBA-15复合分子筛的制备及其催化合成叔丁基苯酚的性能[J].石油化工, 2014, 43(7):767-773. http://www.cnki.com.cn/Article/CJFDTOTAL-SYHG201407006.htm XU Xin-long, SHEN Jian. Preparation of β/SBA-15 composite molecular sieves and their catalytic performances of the synthesis of tert-butyl phenol[J]. Petrkchem Technol, 2014, 43(7):767-773. http://www.cnki.com.cn/Article/CJFDTOTAL-SYHG201407006.htm
[12]	KRESGE C T, LEONOWICZ M E, ROTH W J, VARTULI J C, BECK J S. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism[J]. Nature, 1992, 359(22):710-712. https://www.researchgate.net/publication/32016848_Ordered_Mesoporous_Molecular_Sieves_Synthesized_by_Liquid-Crystal_Template_Mechanism
[13]	CUI Q Y, ZHOU Y S, WEI Q, YU G L ZHU L. Performance of Zr^- and P^-modified USY-based catalyst in hydrocracking of vacuum gas oil[J]. Fuel Process Technol, 2013, 106:439-446. doi: 10.1016/j.fuproc.2012.09.010
[14]	GANJALA V S P, NEELI C K P, PRAMOD C V. Eco-friendly nitration of benzenes over zeolite-β-SBA-15 composite catalyst[J]. Catal Commun, 2014, 49:82-86. doi: 10.1016/j.catcom.2014.02.006
[15]	刘炳四, 邱建国, 袁兴东.加氢裂化集总动力学模型的研究[J].石油学报(石油加工), 1994, 10(3):10-18. http://www.cnki.com.cn/Article/CJFDTOTAL-SYHG503.003.htm LIU Bing-si, QIU Jian-guo, YUAN Xing-dong. Study of lumping kinetic model for hydrocracking[J]. Acta Pet Sin (Pet Process Sect), 1994, 10(3):10-18. http://www.cnki.com.cn/Article/CJFDTOTAL-SYHG503.003.htm