高性能负载型催化填料的制备及其性能研究

doi:10.11949/0438-1157.20240548

化工学报 ›› 2024, Vol. 75 ›› Issue (11): 4226-4236.DOI: 10.11949/0438-1157.20240548

• 催化、动力学与反应器 • 上一篇下一篇

高性能负载型催化填料的制备及其性能研究

王清莲¹^,²(), 熊佩芸¹, 韩俏飞¹^,⁴, 叶长燊¹^,², 王红星³, 杨臣¹^,²(), 邱挺¹^,²()

^1.福州大学化工学院，反应精馏福建省高校工程研究中心，福建福州 350108
^2.清源创新实验室，福建泉州 362801
^3.天津科技大学化工与材料学院，天津 300457
^4.中国石化润滑油有限公司润滑脂分公司，天津 300480

收稿日期:2024-05-23 修回日期:2024-06-25 出版日期:2024-11-25 发布日期:2024-12-26
通讯作者: 杨臣,邱挺
作者简介:王清莲（1989—），女，博士，wqlian@fzu.edu.cn
基金资助:
国家自然科学基金项目(22278076);福建省自然科学基金重点项目(2022J02019)

Preparation and performance investigation of high-performance supported catalytic packing

Qinglian WANG¹^,²(), Peiyun XIONG¹, Qiaofei HAN¹^,⁴, Changshen YE¹^,², Hongxing WANG³, Chen YANG¹^,²(), Ting QIU¹^,²()

^1.Fujian Universities Engineering Research Center of Reactive Distillation Technology, College of Chemical Engineering, Fuzhou University, Fuzhou 350108, Fujian, China
^2.Qingyuan Innovation Laboratory, Quanzhou 362801, Fujian, China
^3.College of Chemical Engineering and Materials Science, Tianjin University of Science & Technology, Tianjin 300457, China
^4.Grease Branch, Sinopec Lubricant Co. , Ltd. , Tianjin 300480, China

Received:2024-05-23 Revised:2024-06-25 Online:2024-11-25 Published:2024-12-26
Contact: Chen YANG, Ting QIU

摘要/Abstract

摘要：

在聚多巴胺辅助二次生长法制备负载型催化填料（SCP）基础上，通过多次晶化及碱处理协同改性，开发了高性能SCP制备方法。研究结果表明，SCP的活性组分层负载量随晶化次数增加而线性增长，但过密的活性组分层结构限制了活性位点的利用。四甲基氢氧化铵（TMAOH）处理通过溶解硅原子形成介孔，提高了外比表面积和扩散效率，增强了SCP的催化活性和焦炭容纳能力。在优化的改性条件下，即晶化次数为3次、TMAOH溶液浓度为0.05 mol/L、碱处理温度为80℃、碱处理时间为120 min，SCP活性提升3.74倍。尽管SCP在乙酸环己酯合成中活性有所下降，但通过焙烧再生可恢复活性。环己烯高温聚合产生的积炭是活性降低的主要原因。

关键词: 催化精馏, 催化填料, 反应, 失活, 再生

Abstract:

Based on the preparation of supported catalytic packing (SCP) by polydopamine-assisted secondary growth method, a high-performance SCP preparation method was developed through multiple crystallization and alkali treatment synergistic modification. It was found that the loading of the active component layer on SCP increases linearly with the number of crystallization steps. However, the excessively dense structure of the active component layer hinders the utilization of active sites. Tetramethylammonium hydroxide (TMAOH) treatment, by dissolving silicon atoms to create mesopores, enhances the external specific surface area and diffusion efficiency, thereby improving the catalytic activity and coke accommodation capacity of SCP. Under the optimized modification conditions, that is, with 3 crystallization times, a TMAOH solution concentration of 0.05 mol/L, an alkaline treatment temperature of 80℃, and an alkaline treatment time of 120 min, the activity of SCP is increased by 3.74 times. Although the activity decreases during the synthesis of cyclohexyl acetate from acetic acid and cyclohexene, the activity can be restored through calcination regeneration. The coke resulting from the high-temperature polymerization of cyclohexene is the primary cause of activity reduction.

Key words: catalytic distillation, catalytic packing, reaction, deactivation, regeneration

中图分类号:

TQ 032.4

王清莲, 熊佩芸, 韩俏飞, 叶长燊, 王红星, 杨臣, 邱挺. 高性能负载型催化填料的制备及其性能研究[J]. 化工学报, 2024, 75(11): 4226-4236.

Qinglian WANG, Peiyun XIONG, Qiaofei HAN, Changshen YE, Hongxing WANG, Chen YANG, Ting QIU. Preparation and performance investigation of high-performance supported catalytic packing[J]. CIESC Journal, 2024, 75(11): 4226-4236.

图/表 16

图1 高性能SCP-PDA-n-N或SCP-PDA-n-T制备流程

Fig.1 Flow chart of the preparation of high-performance SCP-PDA-n-N or SCP-PDA-n-T

图2 多次晶化以及碱处理对SCP-PDA活性及稳定性的影响

Fig.2 Effects of multiple crystallization and alkali treatment on the activity and stability of SCP-PDA

图3 晶化次数对SCP催化活性的影响

Fig.3 Effect of crystallization times on the catalytic activities of SCP

图4 不同碱处理条件对SCP-PDA-3-T催化活性的影响

Fig.4 Effect of alkali treatment condition on the catalytic activity of SCP-PDA-3-T

图5 晶化次数对活性组分负载量的影响

Fig.5 Effect of crystallization times on the loading of HZSM-5 coating

图6 碱处理前后SCP粉末的XRD谱图

Fig.6 XRD patterns of zeolite powders from SCP-PDA-3 and SCP-PDA-3-T

图7 SCP-PDA-3和SCP-PDA-3-T不同放大倍数的SEM照片

Fig.7 SEM images with different magnifications of SCP-PDA-3 and SCP-PDA-3-T

图8 SCP-PDA-3和SCP-PDA-3-T的N2吸-脱附表征结果

Fig.8 Characterization results of N2 adsorption-desorption of SCP-PDA-3 and SCP-PDA-3-T

表1 SCP结构特性

Table 1 Textural properties for SCP

SCP	S_micro^①/（m²·g^-1）	S_ext^②/（m²·g^-1）	S_BET^③/（m²·g^-1）	V_micro^④/（cm³·g^-1）	V_meso^⑤/（cm³·g^-1）
SCP-PDA-3	49.5	47.9	97.5	0.0312	0.0102
SCP-PDA-3-U	44.4	9.13	57.5	0.0221	0.0036
SCP-PDA-3-R	50.3	50.4	100.66	0.0323	0.0109
SCP-PDA-3-T	37.9	66.3	104.2	0.0302	0.0114
SCP-PDA-3-T-U	37.0	24.5	67.7	0.0238	0.0090
SCP-PDA-3-T-R	36.1	61.6	98.0	0.0283	0.0113

图9 SCP-PDA-3与SCP-PDA-3-T催化稳定性

Fig.9 The catalytic stabilities of SCP-PDA-3 and SCP-PDA-3-T

图10 SCP在间歇稳定性实验前后及焙烧再生后的N2吸-脱附等温线

Fig.10 N2 adsorption and desorption isotherms of SCPs before and after stability tests and after roasting regeneration

图11 SCP的实物（左）及SEM照片（右）

Fig.11 Pictures (left) and SEM images (right) of SCPs

图12 SCP的TG曲线和FT-IR谱图

Fig.12 Thermogravimetric curves and Fourier transform infrared spectroscopy spectra of SCPs

图13 SCP-PDA-3-T在乙酸与乙醇酯化反应体系的性能测试结果

Fig.13 Performance test results of SCP-PDA-3-T in esterification of acetic acid with ethanol

图14 SCP-PDA-3-T在乙酸与乙醇酯化反应体系重复性实验前后的N2吸-脱附等温线

Fig.14 N2 adsorption and desorption isotherms of SCP-PDA-3-T before and after the reusability test in esterification of acetic acid with ethanol

图15 SCP-PDA-3-T在乙酸与乙醇酯化反应中重复性实验前后的实物（左）及SEM照片（右）

Fig.15 Pictures (left) and SEM images (right) of SCP-PDA-3-T before and after the reusability test in esterification of acetic acid with ethanol

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高性能负载型催化填料的制备及其性能研究

Preparation and performance investigation of high-performance supported catalytic packing

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