Effect of acid and phosphorus composite modification on the catalytic cracking performance of ZSM-5 molecular sieve

doi:10.16085/j.issn.1000-6613.2025-0174

Abstract

Abstract:

ZSM-5 zeolite modified by acid and phosphorus composite (xSPZ5-H) was prepared and characterized by X-ray fluorescence spectroscopy (XRF), X-ray diffraction (XRD), N₂ physical adsorption desorption (BET), ammonia programmed temperature desorption (NH₃-TPD), Al solid-state nuclear magnetic resonance (Al MAS NMR) and X-ray photoelectron spectroscopy (XPS). Its performance was investigated by catalytic cracking of n-heptane. The results showed that the cracking performance of xSPZ5-H was significantly better than that of the ZSM-5 molecular sieve modified with phosphorus (PZ5-H). This was because the microporous specific surface area and average pore size of xSPZ5-H were significantly larger than those of PZ5-H, which promoted the diffusion of phosphorus species into the pore channels of the molecular sieve during the hydrothermal process, enhanced the coordination ability between phosphorus and framework aluminum, and thereby increased the acidity and hydrothermal stability of the molecular sieve. Compared with PZ5-H zeolite, 1.0SPZ5-H zeolite gave an increased conversion rate from 73.70% to 86.38%, yield of liquefied gas increased from 47.25% to 53.24% and yield of diene increased from 29.49% to 38.08%, demonstrating excellent catalytic performance.

Key words: zeolite, n-heptane, catalytic, phosphorus modification, stability

摘要：

制备了经过酸和磷复合改性的ZSM-5分子筛，采用X射线荧光光谱（XRF）、X射线衍射（XRD）、N₂物理吸脱附（BET）、氨气程序升温脱附（NH₃-TPD）、Al固体核磁共振（Al MAS NMR）和X射线光电子能谱（XPS）对分子筛进行了表征，并将其用于正庚烷催化裂解反应考察其性能。结果表明，经水热处理后酸和磷复合改性的ZSM-5分子筛裂解性能显著优于磷改性的ZSM-5分子筛，这是因为经酸和磷复合改性分子筛xSPZ5-H的微孔比表面积和平均孔径明显高于磷改性分子筛PZ5-H，促进了水热过程中磷物种向分子筛孔道内扩散，增强了磷和四配位骨架铝配位的能力，进而提高了分子筛的酸量和水热稳定性。与磷改性PZ5-H分子筛相比，1.0SPZ5-H分子筛的转化率从73.70%增加至86.38%，液化气收率从47.25%增加至53.24%，双烯收率从29.49%增加至38.08%，表现出优异的催化性能。

关键词: 分子筛, 正庚烷, 催化, 磷改性, 稳定性

CLC Number:

TQ426.94

MA Xiaobiao, LIU Han, WANG Weihuan, MIAO Peipei, JI Yinghui, CHEN Boyang, PENG Xiaowei, XU Qiang, JIN Fengying, MA Mingchao, WANG Yinbin, GUO Chunlei. Effect of acid and phosphorus composite modification on the catalytic cracking performance of ZSM-5 molecular sieve[J]. Chemical Industry and Engineering Progress, 2025, 44(S1): 197-204.

马晓彪, 刘晗, 王伟欢, 苗培培, 季莹辉, 陈博阳, 彭晓伟, 许强, 靳凤英, 马明超, 王银斌, 郭春垒. 酸和磷复合改性对ZSM-5分子筛催化裂解性能的影响[J]. 化工进展, 2025, 44(S1): 197-204.

Figures/Tables 12

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样品名称	组成（质量分数）/%				SiO₂/Al₂O₃	相对结晶度/%
样品名称	SiO₂	Al₂O₃	P₂O₅	SO₃	SiO₂/Al₂O₃	相对结晶度/%
Z5	93.7	5.98	—	—	26.6	100
Z5-H	93.7	5.98	—	—	26.6	68.2
PZ5-H	88.9	5.70	5.03	—	26.5	76.1
0.2SPZ5-H	88.8	5.58	5.02	0.004	27.1	78.5
0.5SPZ5-H	88.9	5.59	5.01	0.005	27.0	82.6
1.0SPZ5-H	89.4	5.54	5.02	0.005	27.4	88.3
2.0SPZ5-H	89.4	5.53	5.01	0.005	27.5	87.8

样品名称	组成（质量分数）/%				SiO₂/Al₂O₃	相对结晶度/%
样品名称	SiO₂	Al₂O₃	P₂O₅	SO₃	SiO₂/Al₂O₃	相对结晶度/%
Z5	93.7	5.98	—	—	26.6	100
Z5-H	93.7	5.98	—	—	26.6	68.2
PZ5-H	88.9	5.70	5.03	—	26.5	76.1
0.2SPZ5-H	88.8	5.58	5.02	0.004	27.1	78.5
0.5SPZ5-H	88.9	5.59	5.01	0.005	27.0	82.6
1.0SPZ5-H	89.4	5.54	5.02	0.005	27.4	88.3
2.0SPZ5-H	89.4	5.53	5.01	0.005	27.5	87.8

样品名称	比表面积/m²·g^-1			孔体积/cm³·g^-1		平均孔径/nm
样品名称	总比表面积	微孔比表面积	介孔比表面积	总孔体积	微孔体积	平均孔径/nm
Z5	300	227	73	0.17	0.12	1.25
Z5-H	291	138	153	0.16	0.06	1.38
PZ5-H	288	69	219	0.14	0.04	1.16
0.2SPZ5-H	291	72	219	0.15	0.04	1.18
0.5SPZ5-H	288	75	213	0.16	0.04	1.21
1.0SPZ5-H	290	83	207	0.16	0.04	1.24
2.0SPZ5-H	287	85	202	0.16	0.04	1.24

样品名称	比表面积/m²·g^-1			孔体积/cm³·g^-1		平均孔径/nm
样品名称	总比表面积	微孔比表面积	介孔比表面积	总孔体积	微孔体积	平均孔径/nm
Z5	300	227	73	0.17	0.12	1.25
Z5-H	291	138	153	0.16	0.06	1.38
PZ5-H	288	69	219	0.14	0.04	1.16
0.2SPZ5-H	291	72	219	0.15	0.04	1.18
0.5SPZ5-H	288	75	213	0.16	0.04	1.21
1.0SPZ5-H	290	83	207	0.16	0.04	1.24
2.0SPZ5-H	287	85	202	0.16	0.04	1.24

样品名称	弱酸		强酸		总酸量 /mmol·g^-1
样品名称	温度/℃	酸量/mmol·g^-1	温度/℃	酸量/mmol·g^-1	总酸量 /mmol·g^-1
Z5	205	0.82	418	0.77	1.59
Z5-H	160	0.04	276	0.04	0.08
PZ5-H	164	0.08	270	0.05	0.13
0.2SPZ5-H	163	0.11	270	0.05	0.16
0.5SPZ5-H	162	0.11	270	0.06	0.17
1.0SPZ5-H	166	0.11	270	0.07	0.18
2.0SPZ5-H	163	0.12	270	0.06	0.18