ZSM-22分子筛合成及其正十二烷烃临氢异构化性能：模板剂和动态晶化的影响

doi:10.16085/j.issn.1000-6613.2023-0211

摘要/Abstract

摘要：

以二乙胺（DEA）或1,6-己二胺（DAH）为模板剂，分别在静态或动态条件下合成具有不同形貌和聚集状态的ZSM-22分子筛，采用XRD、SEM、EDS、TEM、NH₃-TPD及N₂吸附/脱附表征手段对其进行表征分析。并负载Pt在Al₂O₃上和ZSM-22机械混合制备双功能催化剂，考察其正十二烷的临氢异构化反应性能。结果表明，模板剂和动态晶化会改变ZSM-22分子筛的形貌及聚集状态，并且会影响其酸性、比表面积和临氢异构活性。其中，以二乙胺为模板剂，静态晶化72h合成的ZSM-22具有最优的催化性能，在310℃反应温度下，正十二烷异构化转化率为66%时，异构十二烷的选择性达到90%。但是，模板剂及动态晶化条件对单支链异构体的产物分布影响较小，异构体产物以支链靠近端位的2-甲基十一烷为主，且随着反应温度升高，2-甲基异构体选择性明显降低。

关键词: 催化剂, 沸石, 分子筛, ZSM-22, 正十二烷, 临氢异构化

Abstract:

ZSM-22 zeolites with different morphologies and aggregation states were synthesized by using diethylamine (DEA) or 1,6-hexadiamine (DAH) as templates under static or dynamic conditions, respectively, and characterized by XRD, SEM, EDS, TEM, NH₃-TPD and N₂adsorption/desorption. The bifunctional catalyst was prepared by mechanical mixing Pt loaded Al₂O₃ with ZSM-22, and its n-dodecane hydroisomerization performance was investigated. The results showed that template agent and dynamic crystallization could change the morphology and aggregation state of ZSM-22 molecular sieve, and affect its acidity, specific surface area and hydroisomerization activity. ZSM-22 synthesized with diethylamine as template and after 72h of static crystallization had the best catalytic performance. At 310℃, the selectivity of isomerization of n-dodecane reached 90% when the conversion of isomerization was 66%. However, the template agent and the dynamic crystallization conditions had little effect on the distribution of the single branched isomer in product. The isomer products were dominated by 2-methylundecane with the branched chain near the end, and the selectivity of 2-methyl isomer decreased with the increase of reaction temperature.

Key words: catalyst, zeolite, molecular sieves, ZSM-22, n-dodecane, hydroisomerization

中图分类号:

TQ09

张海鹏, 王树振, 马梦茜, 张巍, 向江南, 王玉婷, 王琰, 范彬彬, 郑家军, 李瑞丰. ZSM-22分子筛合成及其正十二烷烃临氢异构化性能：模板剂和动态晶化的影响[J]. 化工进展, 2024, 43(1): 414-421.

ZHANG Haipeng, WANG Shuzhen, MA Mengxi, ZHANG Wei, XIANG Jiangnan, WANG Yuting, WANG Yan, FAN Binbin, ZHENG Jiajun, LI Ruifeng. Synthesis of ZSM-22 molecular sieve and its n-dodecane hydroisomerization performance: Effect of template agent and dynamic crystallization[J]. Chemical Industry and Engineering Progress, 2024, 43(1): 414-421.

图/表 12

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样品	w_atom/%		硅铝比
样品	Si	Al	硅铝比
D-ZSM-22	96.4	3.6	26.8
C-ZSM-22	95.7	4.3	22.3
J-ZSM-22	96.1	3.9	24.6
Z-ZSM-22	96.2	3.8	25.3

样品	w_atom/%		硅铝比
样品	Si	Al	硅铝比
D-ZSM-22	96.4	3.6	26.8
C-ZSM-22	95.7	4.3	22.3
J-ZSM-22	96.1	3.9	24.6
Z-ZSM-22	96.2	3.8	25.3

样品	弱酸量/μmol·g^-1	强酸量/μmol·g^-1	总酸量/μmol·g^-1
D-ZSM-22	181	231	412
C-ZSM-22	185	245	430
J-ZSM-22	196	250	446
Z-ZSM-22	197	253	450

样品	弱酸量/μmol·g^-1	强酸量/μmol·g^-1	总酸量/μmol·g^-1
D-ZSM-22	181	231	412
C-ZSM-22	185	245	430
J-ZSM-22	196	250	446
Z-ZSM-22	197	253	450

样品	总比表面积/m²·g^-1	微孔表面积/m²·g^-1	介孔表面积/m²·g^-1	总孔体积/cm³·g^-1	微孔体积/cm³·g^-1	介孔体积/cm³·g^-1
D-ZSM-22	247	230	17	0.12	0.09	0.03
C-ZSM-22	292	246	46	0.17	0.10	0.07
J-ZSM-22	278	224	54	0.19	0.09	0.10
Z-ZSM-22	279	220	59	0.21	0.09	0.12