纤维状BPO4/SiO2催化剂的制备及其丙烷氧化脱氢性能

doi:10.11949/0438-1157.20210721

摘要/Abstract

摘要：

通过静电纺丝法制备了一种高温焙烧后具有纤维状结构的磷酸硼/二氧化硅（BPO₄/SiO₂）催化剂，并考察了BPO₄负载量和焙烧温度对该催化剂的结构和催化丙烷氧化脱氢性能的影响。研究发现焙烧过程使纤维直径减小。随着BPO₄负载量的增加，丙烷氧化脱氢活性增高。当BPO₄负载量为7%（质量分数），焙烧温度为600℃时，BPO₄/SiO₂催化剂具有最佳的催化性能；在反应温度为480℃下，丙烷转化率和丙烯产率分别达到17.0%和13.0%，且催化剂稳定性良好。当焙烧温度较低时（550℃），催化剂中的有机物分子未被除尽，导致烯烃的选择性偏低；当焙烧温度较高时（700℃），SiO₂结构收缩紧密，抑制了活性相的暴露。由于纤维结构可暴露更多活性位点，该催化剂较相同条件下粉末状BPO₄催化剂有着更高的催化活性。

关键词: 烷烃, 氧化脱氢, 纤维, 纳米结构, 静电纺丝, 催化剂, 磷酸硼

Abstract:

A boron phosphate/silica oxide (BPO₄/SiO₂) catalyst with fibrous structure after calcination was prepared by electrospinning. The effects of BPO₄ loadings and calcination temperatures of the catalysts on the structure and catalytic performance for oxidative dehydrogenation of propane (ODHP) were investigated. Studies have found that the calcination process reduces the fiber diameter. With the increase of BPO₄ loading, the activity of propane oxidative dehydrogenation increased. The BPO₄/SiO₂ catalyst calcined at 600℃ with BPO₄ loading of 7%(mass) showed the best catalytic performance for ODHP. The conversion rate of propane and the yield of propylene for the catalyst at the reaction temperature of 480℃ reached 17.0% and 13.0%, respectively. Meanwhile, the stability test indicated that the catalyst was stable during the reaction. The results showed that when the calcination temperature was low (550℃), the organic molecules in the catalysts were not completely removed, resulting in low olefin selectivity. However, the SiO₂ structure shrank tightly and inhibited the exposure of the active phase with the high calcination temperature (700℃). The catalytic activity of the nanofibrous catalyst was much higher than the conventional bulk BPO₄ catalyst at the same conditions, demonstrating that the structure could expose more active sites.

Key words: alkanes, oxidative dehydrogenation, fiber, nano-structure, electrospinning, catalyst, boron phosphate

中图分类号:

TQ 343

丁鼎, 陆文多, 侯璐, 陆安慧. 纤维状BPO₄/SiO₂催化剂的制备及其丙烷氧化脱氢性能[J]. 化工学报, 2021, 72(11): 5590-5597.

Ding DING, Wenduo LU, Lu HOU, Anhui LU. Preparation of fibrous BPO₄/SiO₂ catalyst for oxidative dehydrogenation of propane[J]. CIESC Journal, 2021, 72(11): 5590-5597.

图/表 8

图1 纺丝薄膜的制备过程

Fig.1 The preparation process of spinning film

图2 BPO4(7%)/SiO2纤维状催化剂的SEM（包括纤维直径分布）照片

Fig.2 SEM images of BPO4(7%)/SiO2 nanofibrous catalyst (inset are fiber diameter distributions)

图3 未焙烧和不同焙烧温度的BPO4(3%)/SiO2纤维状催化剂的FT IR谱图

Fig.3 FT IR spectra of BPO4(3%)/SiO2 nanofibrous catalysts before calcined and at different calcination temperatures

图4 不同BPO4负载量的BPO4/SiO2纤维状催化剂的FT IR和XRD谱图

Fig.4 FT IR spectra and XRD patterns of BPO4/SiO2 nanofibrous catalysts with different BPO4 loadings

图5 经过不同温度焙烧的BPO4(3%)/SiO2的催化性能 (反应条件: 16.7%（体积分数） C3H8, 25.0%（体积分数） O2, 58.3% （体积分数）N2; V总流量 = 12 ml·min-1)

Fig.5 Catalytic performance of BPO4(3%)/SiO2 nanofibrous catalysts calcined at different temperatures (reaction conditions: 16.7%(vol) C3H8, 25.0%(vol) O2, 58.3%(vol) N2; total flow rate 12 ml·min-1)

图6 不同BPO4负载量的BPO4/SiO2纤维状催化剂的催化性能 (反应条件: 16.7%（体积分数） C3H8, 25.0%（体积分数） O2, 58.3%（体积分数） N2; V总流量 = 12 ml·min-1)

Fig.6 Catalytic performance of BPO4/SiO2 nanofibrous catalysts with different BPO4 loadings (reaction conditions: 16.7%（vol） C3H8, 25.0%（vol） O2, 58.3%（vol） N2; total flow rate 12 ml·min-1)

图7 BPO4(7%)/SiO2纤维状和BPO4体相催化剂性能比较 (反应条件: 16.7% C3H8, 25.0% O2, 58.3% N2; V总流量 = 12 ml·min-1)

Fig.7 Comparison of the catalytic property of BPO4/SiO2 nanofibrous catalyst and the bulk BPO4 catalyst (reaction conditions: 16.7% C3H8, 25.0% O2, 58.3% N2; total flow rate 12 ml·min-1)

图8 480℃下BPO4(7%)/SiO2纤维状催化剂的稳定性测试 (反应条件: 反应气, 16.7% C3H8, 25.0% O2, 58.3% N2; V总流量 = 12 ml·min-1)

Fig.8 Catalytic stability tests over BPO4(7%)/SiO2 nanofibrous catalyst at 480℃ (reaction conditions: gas feed, 16.7% C3H8, 25.0% O2, 58.3% N2; total flow rate 12 ml·min-1)

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纤维状BPO₄/SiO₂催化剂的制备及其丙烷氧化脱氢性能

Preparation of fibrous BPO₄/SiO₂ catalyst for oxidative dehydrogenation of propane

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