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

摘要/Abstract

摘要：

本研究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 previously fabricated supported catalytic packing (SCP) by secondary growth method with polydopamine (PDA)-assisted seeding, this work developed a high-performance SCP preparation method through synergistic modification involving multiple crystallization and alkali treatment. 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 minutes, 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:

TQ032.4

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, DOI: 10.11949/0438-1157.20240548.

Qinglian WANG, Peiyun XIONG, Qiaofei HAN, changshen YE, Chen YANG, ting QIU. Preparation and performance investigation of high-performance supported catalytic packing[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240548.

图/表 17

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-PDA-3和SCP-PDA-3-T的结构特性

Table 1 Textural properties of SCP-PDA-3 and SCP-PDA-3-T

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-T	37.9	66.3	104.2	0.0302	0.0114

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

表2 SCP-PDA-3与SCP-PDA-3-T的结构特性

Table. 2 Textural properties of SCP-PDA-3 and SCP-PDA-3-T

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	45.5	34.6	80.1	0.0255	0.0071
SCP-PDA-3-U	40.8	6.6	47.3	0.0181	0.0025
SCP-PDA-3-R	46.3	36.4	82.7	0.0264	0.0076
SCP-PDA-3-T	39.0	46.5	85.5	0.0247	0.0082
SCP-PDA-3-T-U	38.1	17.2	55.6	0.0195	0.0065
SCP-PDA-3-T-R	37.2	43.2	80.4	0.0232	0.0081

图11 SCP的实物（左）及SEM照片（右）

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

图12 SCP的TG曲线和FT-IR图谱

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 (right) images of SCP-PDA-3-T before and after the reusability test in esterification of acetic acid with ethanol

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