沸石孔结构对植物油催化裂化性能的影响

doi:10.16085/j.issn.1000-6613.2021-0631

摘要/Abstract

摘要：

制备出硅铝比相近但介孔体积逐渐增加的超稳Y（USY）沸石，进而制备成微球状催化剂。本文在固定流化床装置上，考察了两种植物油的催化裂化性能。小桐子油的评价结果表明，催化剂中USY沸石的介孔体积越大，汽柴油收率越高；汽油族组成中烯烃收率越高，芳烃收率越低，汽油辛烷值和抗爆指数也越低；采用铵交换和水热改性制备介孔体积为0.142cm³/g的USY沸石催化剂的裂化产物中，汽柴油总收率为62.21%（质量分数），焦炭收率最低，汽油研究法辛烷值达到90.5；大豆油的催化裂化反应规律与小桐子油的一致，中等介孔催化剂裂化得到的汽油研究法辛烷值达到92.2。研究结果表明，采用催化裂化工艺，利用适当介孔的USY沸石催化剂，可以将植物油高效转化为车用轻质燃料，并且得到高辛烷值的汽油。

关键词: 沸石, 离子交换, 催化, 催化剂

Abstract:

USY zeolites with similar framework SiO₂/Al₂O₃ ratio and increased mesopore volume were prepared, with which globular catalysts were prepared by spray drying. Catalytic cracking of Jatropha curcas L. seed oil (JCO) and soybean oil were performed in a constrained fluidized bed reactor. The results of JCO evaluation showed that the gasoline/diesel yields increased as the increased catalyst’s mesopore volume. The higher the yield of olefins and lower yield of aromatics in gasoline gave rise to lower octane number and the anti-explosion index. As for the product distribution of USY catalyst with mesopore volume of 0.142cm³/g, which was prepared by ammonium exchange and hydrothermal modification, the maximum yield of gasoline/diesel was 62.21% (mass fraction), the yield of coke was lowest, and the research octane number (RON) of gasoline was up to 90.5. The catalytic cracking of soybean oil gave the same reaction trend as that of JCO, and the RON of gasoline was up to 92.2 using the catalyst with moderate mesopore volume. The results showed that the catalytic cracking process, with appropriate mesoporous USY zeolite catalyst, can high-efficiently produce light vehicle fuel and high-octane gasoline from vegetable oil.

Key words: zeolite, ion exchange, catalysis, catalyst

中图分类号:

TQ519

郑庆庆. 沸石孔结构对植物油催化裂化性能的影响[J]. 化工进展, 2022, 41(2): 750-758.

ZHENG Qingqing. Influence of pore structure of USY zeolite on its performance in catalytic cracking of vegetable oil[J]. Chemical Industry and Engineering Progress, 2022, 41(2): 750-758.

图/表 18

参考文献 37

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沸石	相对结晶度/%	骨架硅铝比	Na₂O/%	SiO₂/%	Al₂O₃/%
USY_A	80	14.88	0.464	76.1	23.1
USY_B	81	14.90	0.663	76.0	23.0
USY_C	82	14.79	0.698	74.6	24.4
USY_D	80	15.12	0.630	72.7	26.1
USY_E	75	15.08	0.900	70.2	28.6

沸石	相对结晶度/%	骨架硅铝比	Na₂O/%	SiO₂/%	Al₂O₃/%
USY_A	80	14.88	0.464	76.1	23.1
USY_B	81	14.90	0.663	76.0	23.0
USY_C	82	14.79	0.698	74.6	24.4
USY_D	80	15.12	0.630	72.7	26.1
USY_E	75	15.08	0.900	70.2	28.6

沸石	BET比表面积/m²·g^-1	微孔面积/m²·g^-1	介孔面积/m²·g^-1	总孔体积/cm³·g^-1	微孔体积/cm³·g^-1	介孔体积/cm³·g^-1
USY_A	622	562	60	0.347	0.242	0.105
USY_B	618	555	63	0.391	0.249	0.142
USY_C	617	540	77	0.428	0.239	0.189
USY_D	600	512	88	0.440	0.246	0.194
USY_E	551	455	96	0.401	0.187	0.214

沸石	BET比表面积/m²·g^-1	微孔面积/m²·g^-1	介孔面积/m²·g^-1	总孔体积/cm³·g^-1	微孔体积/cm³·g^-1	介孔体积/cm³·g^-1
USY_A	622	562	60	0.347	0.242	0.105
USY_B	618	555	63	0.391	0.249	0.142
USY_C	617	540	77	0.428	0.239	0.189
USY_D	600	512	88	0.440	0.246	0.194
USY_E	551	455	96	0.401	0.187	0.214

沸石	骨架四配位铝	非骨架五配位铝	非骨架六配位铝
USY_A	42.9	34.9	22.2
USY_B	51.0	27.4	21.6
USY_C	40.8	38.8	20.4
USY_D	41.0	37.0	22.0
USY_E	43.5	31.7	24.8