羰基化石墨片催化丙烷氧化脱氢制丙烯

doi:10.15541/jim20190040

摘要/Abstract

摘要：

以资源丰富的石墨片为原材料, 通过简单的气相氧化处理制得羰基化石墨片, 并发现羰基化石墨片可以高选择性催化丙烷氧化脱氢制丙烯: 当丙烷转化率为12.4%时, 丙烯的选择性高达73.9%, 且副产物乙烯的选择性为13%。羰基化石墨片优良的烯烃选择性远超利用相同气相氧化处理的碳管, 并且可以媲美目前催化性能最优的六方氮化硼材料。催化剂具有良好的稳定性, 在505 ℃的反应温度下, 经过48 h的氧化脱氢反应测试后, 催化剂性能无明显的衰减。多种表征技术表明: 气相氧化处理不会破坏石墨片的结构, 且保留了石墨自身的高温抗氧化性, 而经过气相氧化处理羰基官能团的比例大幅度提高, 羰基作为活性位与丙烷中的氢原子发生反应, 自身形成羟基而丙烷则转换为丙烯, 羟基在高温下与氧原子反应生成为羰基, 从而完成催化剂的重生, 继续下一个循环。这种发生在催化剂表面的可控催化方式, 保证了丙烷氧化脱氢过程中选择性生成丙烯, 避免了深度氧化。另外, 石墨材料的来源广泛, 成本低, 作为催化剂可以极大地推动丙烷氧化脱氢的工业化。

关键词: 羰基, 石墨片, 氧化脱氢, 丙烷, 丙烯

Abstract:

Using earth abundant graphite sheets as raw material, carbonyl groups modified graphite sheets were prepared via a simple gaseous-phase oxidation strategy. As-prepared carbonyl groups modified graphite sheets catalyzed oxidative dehydrogenation of propane (ODHP) to propene with high target product selectivity: the product contains 73.9% propene and 13% ethene when the propane conversion is 12.4%. Its high target product selectivity was much better than carbon nanotube that treated by gaseous-phase oxidation, and could compare favorably with the state-of-the-art hexagonal boron nitride catalysts. After 48 h stability test at 505 ℃, there was no obvious variation in the propane conversion and olefins selectivity, demonstrating the remarkable stability of the carbonyl groups modified graphite sheets catalysts. The characterization results revealed that gaseous-phase oxidation didn’t destroy the structure of graphite sheets and inherit the nature of high thermal stability against oxidation. The content of carbonyl groups increased significantly after gaseous-phase oxidation treatment. As active sites, carbonyl groups could abstract the hydrogen atoms from propane and form hydroxyl groups. Hydroxyl groups could react with oxygen atom and regenerate to carbonyl group. The high target product selectivity can be attributed to the controllable reaction style on catalyst surface. Furthermore, graphite sheets are rich in resource and low cost. As a catalyst, it would promote the industrialization of ODHP.

Key words: carbonyl group, graphite sheet, oxidative dehydrogenation, propane, propene

中图分类号:

O643

曹磊, 代鹏程, 刘丹丹, 顾鑫, 李良军, 赵学波. 羰基化石墨片催化丙烷氧化脱氢制丙烯[J]. 无机材料学报, 2019, 34(11): 1187-1192.

CAO Lei, DAI Peng-Cheng, LIU Dan-Dan, GU Xin, LI Liang-Jun, ZHAO Xue-Bo. Carbonyl Groups Modified Graphite Sheets Catalyze Oxidative Dehydrogenation of Propane to Propene[J]. Journal of Inorganic Materials, 2019, 34(11): 1187-1192.

图/表 9

图1 羰基化石墨片在高纯空气气氛下的TGA曲线

Fig. 1 TGA curve of carbonyl groups graphite sheets tested at high purity air

图2 (a)丙烷转化率和产物选择性随反应温度的变化曲线和(b)烯烃的收率随丙烷转化率的变化曲线

Fig. 2 Catalytic performance of ODHP over the carbonyl groups graphite sheets as a function of reaction temperature (a), and olefins yield as a function of propane conversion (b)

图3 羰基化石墨片催化丙烷氧化脱氢制烯烃的稳定性(a)和碳平衡(b)

Fig. 3 Stability (a) and carbon balance during the catalytic test (b) of carbonyl groups graphite sheets for ODHP over 48 h

图4 羰基化石墨片催化丙烷氧化脱氢制烯烃测试前后的SEM照片

Fig. 4 SEM images of carbonyl groups graphite sheets before (fresh) and after (spent) ODHP test (a, b) Fresh; (c, d) Spent

图5 羰基化石墨片催化丙烷氧化脱氢反应前后的XRD图谱

Fig. 5 XRD patterns of carbonyl groups graphite sheets before (fresh) and after (spent) ODHP test

图6 羰基化石墨片稳定性测试之后的TEM照片

Fig. 6 TEM images of carbonyl groups graphite sheets after ODHP stability test

图7 羰基化石墨片催化丙烷氧化脱氢反应前后N2吸附-脱附等温线(a)和孔径分布图(b)

Fig. 7 N2 adsorption/desorption isotherms (a) and DFT pore size distribution (b) of carbonyl groups graphite sheets before (fresh) and after (spent) ODHP test

图8 羰基化石墨片催化丙烷氧化脱氢反应前后的红外光谱图

Fig. 8 FT-IR spectra of the carbonyl groups graphite sheets before (fresh) and after (spent) ODHP test

图9 羰基化石墨片催化丙烷氧化脱氢反应前后的XPS谱图(a)和O1s谱图(b)

Fig. 9 XPS spectra (a) and fitting curves of O1s spectra (b) of carbonyl groups graphite sheets before (fresh) and after (spent) ODHP test

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