Preparation and performance investigation of high-performance supported catalytic packing

doi:10.11949/0438-1157.20240548

Abstract

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

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

CLC Number:

TQ 032.4

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.

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.

Figures/Tables 16

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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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