ZSM-5分子筛酸性能和孔结构的协同作用对C5烯烃催化裂解性能的影响

doi:10.11949/0438-1157.20221200

摘要/Abstract

摘要：

采用不同浓度碱液处理制备了具有不同酸性质的多级孔HZSM-5分子筛，并考察其酸性能与孔结构变化对催化裂化(FCC)汽油中C₅烯烃催化裂解性能的影响。利用X射线衍射(XRD)、N₂吸附脱附、氨气程序升温脱附技术(NH₃-TPD)、吡啶红外(Py-IR)和扫描电镜(SEM)等表征手段研究了HZSM-5分子筛的结构、形貌、酸性质和孔道性能。研究结果表明，适宜浓度的碱液处理可以提高HZSM-5分子筛的强Brønsted (B酸)酸量和介孔体积，显著提高C₅烯烃转化率和乙烯、丙烯的收率。当碱液浓度为0.2 mol·L^-1，HZSM-5分子筛强B酸中心和介孔体积之间的协同作用促进了C₅烯烃的高效转化，转化率为84.8%(质量分数)，乙丙烯总收率为86.0%(质量分数)，分别比未处理的HZSM-5分子筛增加4.4%和15.5%。

关键词: 碱处理, ZSM-5分子筛, 催化裂解, 低碳烯烃

Abstract:

Hierarchical pore HZSM-5 zeolite with different acid properties was prepared by using alkali treatment with different concentrations, and the effect of their pore properties on the catalytic cracking performance of C₅ olefins in FCC gasoline was investigated. The structure, morphology, acid properties and pore properties of HZSM-5 zeolite were investigated using XRD, N₂ adsorption desorption, ammonia programmed temperature desorption technique (NH₃-TPD), pyridine infrared (Py-IR), and scanning electron microscopy (SEM) characterization. The results showed that the appropriate concentration of alkali treatment could increase the amount of strong B acid site and mesopore volume of HZSM-5 zeolite, and significantly increase the conversion of C₅ olefins and the yields of ethylene and propylene. When the alkali concentration was 0.2 mol·L^-1, the synergistic effect between the strong B acid site and mesopore volume of HZSM-5 zeolite promoted the efficient conversion of C₅ olefins, the conversion rate was 84.8% (mass), and the total yield of ethylene-propylene was 86.0% (mass), which was 4.4% and 15.5% higher than that of the untreated HZSM-5 zeolite, respectively.

Key words: alkali treatment, ZSM-5 zeolite, catalytic cracking, light olefins

中图分类号:

O 643.3

白宇恩, 张彬瑞, 刘东阳, 赵亮, 高金森, 徐春明. ZSM-5分子筛酸性能和孔结构的协同作用对C₅烯烃催化裂解性能的影响[J]. 化工学报, 2023, 74(1): 438-448.

Yuen BAI, Binrui ZHANG, Dongyang LIU, Liang ZHAO, Jinsen GAO, Chunming XU. Influence of synergistic effect of acid properties and pore structure of ZSM-5 zeolite on the catalytic cracking performance of pentene[J]. CIESC Journal, 2023, 74(1): 438-448.

图/表 16

图1 实验装置流程1—原料油罐;2—进料泵1;3—原料水罐;4—进料泵2;5—进液压力表;6—稳压阀;7—气体压力表;8—气体流量计;9—预加热炉;10—反应管;11—加热炉;12—反应压力表;13—备压阀;14—螺旋冷凝罐;15—储液罐;16—液体接样口;17—循环冷凝装置;18—气体接样口

Fig.1 The experimental equipment

表1 原料汽油组成（质量分数）

Table 1 The composition （mass fraction） of raw gasoline

C number	nP/%	iP/%	O/%	N/%	A/%	C sum/%
4	1.69	0.85	3.60	0	0	6.14
5	4.87	25.82	38.56	0.38	0	69.63
6	0.94	14.01	7.38	0.75	0.20	23.28
7	0.03	0.29	0.29	0.03	0.10	0.74
8	0	0	0	0	0.15	0.15
9	0	0	0	0	0.09	0.09
total	7.53	40.97	49.83	1.15	0.54	100.00

图2 不同浓度碱液处理HZSM-5的XRD谱图

Fig.2 XRD patterns of HZSM-5 treated with different concentrations of alkali

图3 不同浓度碱液处理HZSM-5的N2吸附-脱附等温曲线

Fig.3 N2 adsorption-desorption isothermal curves of HZSM-5 treated with different concentrations of alkali

图4 不同浓度碱液处理HZSM-5的孔径分布

Fig.4 Pore size distribution of HZSM-5 treated with different concentrations of alkali

表2 不同浓度碱液处理HZSM-5的孔数据

Table 2 Pore data of HZSM-5 treated with different concentrations of alkali

Sample	Surface area/（m²·g^-1）	Rate of change/%	Pore volume/（cm³·g^-1）			D_pore/nm
Sample	Surface area/（m²·g^-1）	Rate of change/%	Total	Micropore	Mesopore	D_pore/nm
HZSM-5	273	—	0.17	0.12	0.05	2.46
AT1	322	17.95	0.19	0.12	0.07	2.38
AT2	321	17.58	0.20	0.12	0.08	2.46
AT3	323	18.32	0.19	0.12	0.07	2.40
AT4	305	11.72	0.24	0.10	0.14	2.73
AT5	303	10.99	0.26	0.09	0.17	3.10

图5 不同浓度碱液处理的HZSM-5样品的SEM图

Fig.5 SEM images of HZSM-5 samples treated with different concentrations of alkali

图6 不同浓度碱液处理的HZSM-5样品的mapping图

Fig.6 Mapping images of HZSM-5 samples treated with different concentrations of alkali

图7 不同浓度碱液处理后的HZSM-5的Py-IR谱图

Fig.7 Py-IR spectra of HZSM-5 treated with different concentrations of alkali

表3 不同浓度碱液处理后的HZSM-5的Py-IR数据

Table 3 Py-IR data of HZSM-5 treated with different concentrations of alkali

Sample	Total acid（200℃）			Strong acid（350℃）		Weak acid
Sample	（L+B）/(μmol·g^-1)	L/(μmol·g^-1)	B/(μmol·g^-1)	L/(μmol·g^-1)	B/(μmol·g^-1)	L/(μmol·g^-1)	B/(μmol·g^-1)
HZSM-5	209.87	165.83	44.04	58.86	9.39	106.97	34.65
AT1	176.12	139.98	36.14	70.21	9.78	69.77	26.36
AT2	194.76	158.80	35.96	85.68	10.50	73.12	25.46
AT3	223.01	178.85	44.16	75.17	14.59	103.68	29.57
AT4	218.30	178.54	39.76	93.88	13.68	84.66	26.08
AT5	189.02	139.74	49.28	66.82	10.11	72.92	39.17

图8 不同浓度碱液处理后的HZSM-5的NH3-TPD谱图

Fig.8 NH3-TPD spectra of HZSM-5 treated with different concentrations of alkali

图9 碱液处理前后HZSM-5的烯烃收率和选择性

Fig.9 Yield and selectivity of HZSM-5 before and after alkali treatment

图10 碱液处理前后HZSM-5的副产物选择性

Fig.10 HZSM-5 by-product selectivity before and after alkali treatment

图11 不同浓度碱处理HZSM-5的烯烃收率和选择性

Fig.11 Yield and selectivity of HZSM-5 treated with different concentrations of alkali

图12 不同浓度碱处理HZSM-5的副产物选择性

Fig.12 Selectivity of by-products of HZSM-5 treated with different concentrations of alkali

图13 不同浓度碱液处理HZSM-5的指数图

Fig.13 Index chart of HZSM-5 treated with different concentrations of alkali

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ZSM-5分子筛酸性能和孔结构的协同作用对C₅烯烃催化裂解性能的影响

Influence of synergistic effect of acid properties and pore structure of ZSM-5 zeolite on the catalytic cracking performance of pentene

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