微波强化Y型分子筛离子交换技术

doi:10.11949/0438-1157.20210169

摘要/Abstract

摘要：

近年来，随着微波技术的快速发展，微波能作为一种高效的清洁能源已在化工合成、工业催化、生物制药、食品加工等众多领域广泛应用。尤其是在化工合成领域，微波技术的应用展现出了高效加热、易于控制、安全环保的优势。采用微波辅助技术对NaNH₄Y分子筛与稀土溶液热压离子交换反应进行研究，进一步开发出了无须经高温焙烧工序短流程工艺制备稀土Y分子筛的工艺技术。相比于分子筛传统工业制备技术，大大缩短了制备工艺流程，极大提高了分子筛离子交换改性生产效率并降低了生产能耗。开发的新工艺技术制备的稀土Y分子筛，主要物化性质参数满足工业生产同类型分子筛产品工艺质量指标要求，且制备的分子筛催化剂活性稳定性均不低于传统工业生产分子筛催化剂。新工艺方法对优化催化裂化分子筛工业生产和实现分子筛的短流程工业制备具有重要指导意义。

关键词: 微波加热, 分子筛, 离子交换, 水热, 催化剂, 短流程

Abstract:

In recent years, with the rapid development of microwave technology, microwave energy as an efficiently clean energy has been widely used in many fields, such as chemical synthesis, industrial catalysis, biopharmaceuticals, food processing, etc. Especially in the field of chemical synthesis, microwave technology shows obvious advantages of high efficiency, easy control, safety, and no pollution. In this work, microwave-assisted technology is utilized to investigate the hydrothermal ion exchange reaction between NaNH₄Y molecular sieve and rare earth solution and develops the method of synthesis REY molecular sieve without high-temperature roasting process. Compared with the traditional industrial preparation methods of rare earth-containing molecular sieve, the preparation process is greatly shortened, the production efficiency of molecular sieve ion exchange process is greatly improved, and the production energy consumption is reduced. The main physical and chemical property parameters of REY molecular sieve prepared by the developed new method meet the quality index requirements of the same type of molecular sieves in industrial production, and the activity stability of the prepared catalyst is not lower than that of the traditional industrial molecular sieve catalyst. The process method studied in this work has important guiding significance for optimizing the industrial production of catalytic cracking molecular sieves and realizing the short-process industrial preparation of molecular sieves.

Key words: microwave heating, molecular sieve, ion exchange, hydrothermal, catalyst, short-process

中图分类号:

TQ 028

李腾飞, 缪赟, 杨柳, 王龙耀, 朱铧丞. 微波强化Y型分子筛离子交换技术[J]. 化工学报, 2021, 72(S1): 406-412.

LI Tengfei, MIAO Yun, YANG Liu, WANG Longyao, ZHU Huacheng. Microwave enhanced ion exchange technology of Y molecular sieve[J]. CIESC Journal, 2021, 72(S1): 406-412.

图/表 9

表1 分子筛的理化性质

Table 1 Physicochemical properties of molecular sieves

化合物	平均粒径/nm	Na₂O质量分数/%	SiO₂/Al₂O₃摩尔比	相对结晶/%	总比表面积/(m²/g)	总孔体积/(ml/g)	骨架坍塌温度/℃
NaY	1000	12.71	5.2	88	750	0.415	928
NaNH₄Y	980	3.85	5.2	86	648	0.310	985

图1 稀土Y分子筛制备工艺流程

Fig.1 Preparation process of REY molecular sieve

图2 分子筛催化剂制备工艺流程

Fig.2 Preparation process of FCC catalyst

表2 NaNH4Y分子筛水热离子交换对比试验结果

Table 2 Comparison experimental results of NaNH4Y molecular sieves by hydrothermal ion exchange

交换方法	交换时间/min	Na₂O质量分数/%	Re₂O₃质量分数/%
微波辅助加热（REY-B）	15	1.10	19.97
常规方式加热（REY-A）	60	1.77	18.14
	120	1.32	18.43
	180	1.16	18.85
	240	1.09	19.47

表3 微波辅助水热交换不同交换时间试验结果

Table 3 Experimental results of microwave-assisted hydrothermal exchange at different exchange times

编号	升温时间/min	恒温交换时间/min	Na₂O质量分数/%	Re₂O₃质量分数/%
REY-B-1	15	5	1.27	19.65
REY-B-2	15	10	1.12	19.97
REY-B-3	15	15	1.10	19.80
REY-B-4	15	20	1.06	20.01

图3 水热交换前后分子筛XRD谱图

Fig.3 XRD patterns of molecular sieves before and after hydrothermal ion exchange

图4 分子筛微波辅助热压交换前后SEM图

Fig.4 SEM images of molecular sieves before and after microwave-assisted hydrothermal exchange

表4 分子筛的相对结晶度、晶胞参数、比表面积

Table 4 Relative crystallinity， cell parameters and specific surface area of molecular sieves

分子筛

晶胞常数/nm

相对

结晶度/%

比表面积/

(m²/g)

表5 分子筛催化剂主要理化性质

Table 5 Main physicochemical properties of molecular sieve catalysts

催化剂	Na₂O/%	Cl^-/%	SO₄^2-/%	比表面积/(m²/g)	孔容/(ml/g)	MAT(800℃/4 h)	MAT(800℃/17 h)
催化剂X	0.21	1.27	0.47	261.3	0.28	79.3	62.3
催化剂Y	0.14	0.63	0.59	264.6	0.28	80.0	62.5

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