HZSM-5催化剂改性及其催化苯与低浓度乙烯反应的中试研究

doi:10.19964/j.issn.1006-4990.2022-0443

Abstract

Abstract:

The alkylation of benzene with dilute ethylene to produce ethylbenzene is an efficient route to realize the value-added utilization of dilute ethylene and increase the production of ethylbenzene.The modified HZSM-5 catalysts were prepared by the steam and citric acid post-treatment.The HZSM-5 catalyst samples before and after post-treatment were characterized by X-ray diffraction（XRD），nitrogen physical adsorption desorption，and ammonia temperature programmed desorption（NH₃-TPD）.The pilot-scale catalytic performance for alkylation of benzene with dilute ethylene on HZSM-5 catalysts with different post-treatments was investigated.The results showed that the sequential steam and citric acid treatment significantly adjusted the acid amount and acid strength of the catalyst，and increased the pore volume and pore size of the catalyst，thereby effectively improving the ethyl benzene selectivity and suppressing the side reaction，and also reducing the production of xylene and heavy components.The obviously improved performance was obtained by sequential steam and citric acid treatment on HZSM-5 catalyst，the selectivity of ethyl benzene was increased to 99.0%，and the by-product selectivity of xylene was reduced to 7.7×10^-5，which showed the prospect of industrial application.

Key words: HZSM-5 catalyst, benzene alkylation with ethylene, ethylbenzene, post-treatment

CLC Number:

O643.3

ZHANG Yongkun, CHANG Yang, LI Xiaoguo, LIU Yan, XING Changxin, GAO Jinping, XIAO Jiawang, HOU Zhanggui. Study on modification of HZSM-5 catalyst and its pilot catalytic performance for alkylation of benzene with dilute ethylene[J]. Inorganic Chemicals Industry, 2023, 55(5): 137-142.

Figures/Tables 10

Table 1

Fig.1

Fig.2

Fig.3

Table 2

Fig.4

Table 3

Table 4

Catalytic performance of HZSM-5 catalyst and post-treated catalysts"

催化剂	反应时间/h	C_ethylene/ %	S_ethylbenzene/ %	S_xylene/10^-6	S_toluene/ %	$S C 9 +$ / %
^aZ5-P	48	99.9	97.2	246	0.4	2.2
^bZ5-P	120	99.9	98.1	239	0.3	1.4
^aZ5-ST	48	99.4	98.5	84	0.1	1.3
^bZ5-ST	120	99.9	98.9	69	0.1	0.9
^aZ5-ST-CA	48	99.6	98.5	84	0.2	1.3
^bZ5-ST-CA	120	99.9	99.0	77	0.1	0.9
^aZ5-CA	48	99.9	97.2	246	0.4	2.2
^bZ5-CA	120	99.9	98.0	248	0.3	1.5

Table 4

Fig.5

Fig.6

References 22

1	BIAN Kai， ZHANG Anfeng， YANG Hong，et al.Synthesis and characterization of Fe-substituted ZSM-5 zeolite and its catalytic performance for alkylation of benzene with dilute ethylene[J].Industrial & Engineering Chemistry Research，2020，59（52）：22413-22421.
2	YANG Weimin， WANG Zhendong， SUN Hongmin，et al.Advances in development and industrial applications of ethylbenzene processes[J].Chinese Journal of Catalysis，2016，37（1）：16-26.
3	SHAVALEEV D A， PAVLOV M L， BASIMOVA R A，et al.Synthesis of a zeolite-containing catalyst for gas-phase alkylation of benzene with ethylene[J].Petroleum Chemistry，2020，60（10）：1164-1169.
4	孙洪敏.乙苯生产技术及市场分析[J].石油化工技术与经济，2019，35（5）：18-23.
	SUN Hongmin.Ethylbenzene production technology and market analysis[J].Technology & Economics in Petrochemicals，2019，35（5）：18-23.
5	ZHANG Bin， WANG Zhendong， JI Peng，et al.Efficient liquid-phase ethylation of benzene with ethylene over mesoporous MCM-22 catalyst[J].Microporous and Mesoporous Materials，2013，179：63-68.
6	宦明耀，孙洪敏，张斌，等.改性ZSM-5催化剂上苯与FCC干气中乙烯气相烷基化反应[J].化学反应工程与工艺，2008，24（5）：395-399.
	HUAN Mingyao， SUN Hongmin， ZHANG Bin，et al.Vapor phase alkylation of benzene with ethylene in FCC dry gas over modified ZSM-5 zeolite catalyst[J].Chemical Reaction Engineering and Technology，2008，24（5）：395-399.
7	张丽君，王振东，孙洪敏，等.气相法乙苯清洁生产工艺技术进展[J].工业催化，2016，24（5）：1-7.
	ZHANG Lijun， WANG Zhendong， SUN Hongmin，et al.Advance in ethylbenzene processes through vapor-phase alkylation of benzene[J].Industrial Catalysis，2016，24（5）：1-7.
8	GU Yunfeng， LIU Wenshuai， WANG Ning.Technological progress of ethylbenzene production by alkylation[J].Tianjin Chemical Industry，2022，36（2）：106-109.
9	薛明伟.干气综合利用生产技术进展[J].石油化工技术与经济，2019，35（1）：56-62.
	XUE Mingwei.Progress in production technology of dry gas comprehensive utilization[J].Technology & Economics in Petrochemicals，2019，35（1）：56-62.
10	SHEN Zhenhao， MA Chongwei， HE Junlin，et al.Preparation of a shaped core-shell structured binder-free ZSM-5 catalyst and its application for benzene alkylation with ethylene[J].Applied Catalysis A：General，2019，577（1）：20-27.
11	王文静，武光，吴伟，等.纳米ZSM-5分子筛的酸脱铝改性及其催化萘和甲醇的烷基化反应性能[J].石油学报：石油加工，2014，30（4）：620-628.
	WANG Wenjing， WU Guang， WU Wei，et al.Dealumination of ZSM-5 nanocrystals with different acids and their catalytic performances in methylation of naphthalene with methanol[J].Acta Petrolei Sinica：Petroleum Processing Section，2014，30（4）：620-628.
12	ZHAO Liang， WANG Hongbo， LIU Min，et al.Shape-selective methylation of 2-methylnaphthalene with methanol over hydrothermal treated HZSM-5 zeolite catalysts[J].Chemical Engineering Science，2008，63（21）：5298-5303.
13	RESASCO D E， CROSSLEY S P， WANG Bin，et al.Interaction of water with zeolites：A review[J].Catalysis Reviews，2021，63（2）：302-362.
14	边凯，候章贵，段欣瑞，等.二维HZSM-5纳米片的合成及催化苯与稀乙烯烷基化制乙苯[J].高等学校化学学报，2019，40（4）：784-792.
	BIAN Kai， HOU Zhanggui， DUAN Xinrui，et al.Synthesis and catalytic performance of 2D HZSM-5 nano-sheet for ethylbenzene production from benzene with dilute ethylene[J].Chemical Journal of Chinese Universities，2019，40（4）：784-792.
15	段欣瑞，李孝国，张永坤，等.纳米HZSM-5的酸性调控及其催化苯和稀乙烯制乙苯[J].石油学报：石油加工，2021，37（1）：181-189.
	DUAN Xinrui， LI Xiaoguo， ZHANG Yongkun，et al.Acid modification of nanosized HZSM-5 for alkylation of benzene with dilute ethylene[J].Acta Petrolei Sinica：Petroleum Processing Section，2021，37（1）：181-189.
16	谢卓涵，韩贺，李孝国，等.纳米Ga-ZSM-5分子筛的合成及其在苯和稀乙烯烷基化反应中的应用[J].无机盐工业，2022，54（2）：123-128.
	XIE Zhuohan， HAN He， LI Xiaoguo，et al.Synthesis of nano Ga-ZSM-5 zeolite and its application in alkylation of benzene with dilute ethylene[J].Inorganic Chemicals Industry，2022，54（2）：123-128.
17	FAN Yu， BAO Xiaojun， LIN Xiuying，et al.Acidity adjustment of HZSM-5 zeolites by dealumination and realumination with stea-ming and citric acid treatments[J].The Journal of Physical Che-mistry B，2006，110（31）：15411-15416.
18	毛东森，郭强胜，孟涛，等.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.
	MAO Dongsen， GUO Qiangsheng， MENG Tao，et al.Effect of hydrothermal treatment on the acidity and catalytic performance of nanosized HZSM-5 zeolites for the conversion of methanol to propene[J].Acta Physico-Chimica Sinica，2010，26（2）：338-344.
19	BAERLOCHER C， MCCUSKER L B， OLSON D H.C2/C[M]//Atlas of Zeolite Framework Types.Amsterdam：Elsevier，2007：258- 259.
20	ONG L H， DÖMÖK M， OLINDO R，et al.Dealumination of HZSM-5 via steam-treatment[J].Microporous and Mesoporous Materials，2012，164：9-20.
21	LI Wenlin， LI Feng， WANG Hongyan，et al.Hierarchical mesoporous ZSM-5 supported nickel catalyst for the catalytic hydrodeoxygenation of anisole to cyclohexane[J].Molecular Catalysis，2020，480：110642.
22	王辉，张汉军，孔德金，等.ZSM-5催化剂水蒸汽处理对甲苯选择性歧化性能的影响[J].石油化工，2000，29（6）：401-404.
	WANG Hui， ZHANG Hanjun， KONG Dejin，et al.Effects of hydrothermal treatment on selective toluene disproportionation[J].Petrochemical Technology，2000，29（6）：401-404.

催化剂	S_BET/	S_micro/	S_meso/	V_micro/	V_T/
催化剂	（m²·g^-1）	（m²·g^-1）	（m²·g^-1）	（cm³·g^-1）	（cm³·g^-1）
Z5-P	293	181	112	0.077	0.218
Z5-ST	303	187	116	0.080	0.231
Z5-ST-CA	308	189	119	0.082	0.233
Z5-CA	295	180	115	0.078	0.230

催化剂样品	弱酸峰温度/℃	强酸峰温度/℃	酸量/（μmol·g^-1_cat.）
催化剂样品	弱酸峰温度/℃	强酸峰温度/℃	弱酸	强酸	总酸量
Z5-P	150	360	155.2	97.8	253.1
Z5-ST	142	326	120.8	69.2	190.0
Z5-ST-CA	145	325	104.9	40.6	145.5
Z5-CA	146	350	134.3	88.9	223.2

[1]	XIE Zhuohan,HAN He,LI Xiaoguo,ZHANG Yongkun,HOU Zhanggui,BIAN Kai,ZHANG Anfeng,GUO Xinwen,SONG Chunshan. Synthesis of nano Ga-ZSM-5 zeolite and its application in alkylation of benzene with dilute ethylene [J]. Inorganic Chemicals Industry, 2022, 54(2): 123-128.
[2]	Peng Wenbo,Yun Jianjun,Ding Bangchao,Bai Zuguo,Xiao Weiyi,Wang Xiaohu. Study on membrane integration technology in treatment of wastewater from chlorinated titanium dioxide [J]. Inorganic Chemicals Industry, 2020, 52(6): 76-79.
[3]	Liu Zhikai1，Cao Hui2，Wang Tianyun1，Han Guodong2，Liu Yi1，Zhang Yi1. Study on novel catalysts for direct catalytic conversion of unconventional natural gas to aromatics [J]. Inorganic Chemicals Industry, 2019, 51(12): 83-88.

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Study on modification of HZSM-5 catalyst and its pilot catalytic performance for alkylation of benzene with dilute ethylene

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 10

References 22

Related Articles 3

Metrics

Comments

Recommended 0