Co-YPO4双功能催化剂促进乙醇高值转化制丁二烯

doi:10.1016/S1872-2067(23)64567-X

摘要/Abstract

摘要：

丁二烯是重要的化工原料, 主要用于生产树脂、合成橡胶、丁二醇和己二腈等大宗化学品, 还可以用于制备蒽醌、四氢苯酐等精细化学品. 目前, 工业上制备丁二烯的方法主要是乙烯副产抽提法. 近年来, 随着生物乙醇技术大力发展, 催化乙醇制丁二烯成为很有吸引力的生产丁二烯的路线之一. 目前催化乙醇制丁二烯的催化剂种类较多, 合理设计具有活性位点结构和功能的催化新材料是提升催化剂活性的关键. 稀土金属元素如Y, La和Ce等具有独特的电子层结构, 并且具有中等强度的Lewis酸性, 本文尝试将稀土磷酸盐与具有乙醇脱氢活性的过渡金属位点结合起来, 设计过渡金属改性的稀土磷酸盐催化剂并用于乙醇转化制丁二烯.

本文开发了Co-YPO₄双功能催化剂, 应用于乙醇转化制丁二烯反应, 所制材料表现出较高的催化活性与稳定性. 在YPO₄催化剂上, 乙醇主要发生脱水反应, 生成大量的乙烯和乙醚, 且丁二烯选择性不超过5%; 而在Co-YPO₄催化剂上, 乙醇转化产物分布出现明显改变, 丁二烯选择性增加. 在乙醇重时空速和反应温度分别为1.0 g_C2H5OH•g_Cat.^‒1•h^‒1和350 °C的条件下, 乙醇转化率为78.2%, 丁二烯选择性为68.5%. 原位紫外-可见漫反射光谱、X射线光电子能谱以及H₂-程序升温还原表征结果表明, Co²⁺中心与PO₄^3‒基团存在强的配位相互作用, 形成稳定且高度分散的[Co-O-P]物种. 通过NH₃-程序升温脱附(TPD)和吡啶探针分子吸附红外对YPO₄和Co-YPO₄进行酸性表征, 结果表明, YPO₄和Co-YPO₄表面均是典型的Lewis酸性位点; 结合CO₂-TPD表征发现, Co²⁺与YPO₄表面部分Y³⁺位点发生置换, 即引入适量的Co会减弱酸性同时增强表面碱性. 进一步通过停留时间、乙醇程序升温表面反应和原位乙醇吸附反应漫反射红外光谱测试对反应机理进行详细研究. 结果表明, 乙醇首先在Co²⁺位发生脱氢生成乙醛和H₂, 随后乙醛迁移至Y³⁺位点吸附活化, 两分子乙醛依次发生C‒C偶联、加氢以及脱水反应生成丁二烯. 动力学测试结果表明, 乙醇脱氢是整个反应过程的关键步骤, 整体反应路径如下: 乙醇→乙醛→2-丁烯醛→2-丁烯醇→丁二烯.

综上所述, 以乙醇作为平台分子合成丁二烯能够丰富可持续发展的新能源结构体系. 本文揭示了磷酸根基团通过配位作用稳定Co²⁺物种, Co²⁺和Y³⁺位点协同催化乙醇选择性生成丁二烯, 为乙醇高值转化催化剂设计提供了新思路.

关键词: 乙醇, 丁二烯, 脱氢, 碳碳偶联, 磷酸盐

Abstract:

Upgrading of sustainable ethanol into C₄ olefins by C-C coupling contributes to alleviating the dependency towards petroleum. The reaction network consists several key steps, whereas dehydration often competes with dehydrogenation over acidic catalyst. Herein, we report a designed bifunctional Co-YPO₄ catalyst with balanced active sites for dehydrogenation and condensation that can directly catalyze ethanol to butadiene. The YPO₄ can stabilize Co²⁺ species to form highly dispersed [Co-O-P] sites, which catalyze ethanol dehydrogenation to acetaldehyde. Additionally, the YPO₄ surface exposed Y³⁺ site, as Lewis acid center, which can effectively catalyze C-C coupling reaction. The addition of cobalt enhances the ethanol dehydrogenation process while reducing the surface acidity, thus inhibiting the formation of dehydration products and promoting the formation of butadiene. Kinetic measurements suggest that the rate-limiting step is the dehydrogenation of ethanol to acetaldehyde. The synthesized Co-YPO₄ shows a 68.5% selectivity of butadiene under a conversion of 78.2% at 350 °C and a weight hourly space velocity of 1.0 g_C2H5OH•g_Cat.^-1•h^-1.

Key words: Ethanol, Butadiene, Dehydrogenation, C-C coupling, Phosphate

周百川, 李文翠, 王嘉, 孙丹卉, 向诗煜, 高新芊, 陆安慧. Co-YPO₄双功能催化剂促进乙醇高值转化制丁二烯[J]. 催化学报, 2024, 56: 166-175.

Bai-Chuan Zhou, Wen-Cui Li, Jia Wang, Dan-Hui Sun, Shi-Yu Xiang, Xin-Qian Gao, An-Hui Lu. PO₄^3- coordinated Co²⁺ species on yttrium phosphate boosting the valorization of ethanol to butadiene[J]. Chinese Journal of Catalysis, 2024, 56: 166-175.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64567-X

https://www.cjcatal.com/CN/Y2024/V56/I1/166

图/表 9

Fig. 1. Temperature-dependence of ethanol conversion and products distribution over Co-YPO4 (1.0 wt%) (a), and YPO4 (b). Reaction conditions: 100 mg Co-YPO4 or YPO4, C2H5OH/N2 = 5.7/94.3, WHSV = 2.0 gC2H5OH?gcat-1?h-1. (c) Effect of Co loadings on ethanol conversion and products distribution. (d) Ethanol conversion and the selectivity of butadiene over different catalysts. Reaction conditions: 350 °C, 100 mg catalyst, C2H5OH/N2 = 5.7/94.3, WHSV = 2.0 gC2H5OH?gCat.-1?h-1, Vtotal = 30 mL?min-1.

Fig. 2. Characterization of Co-YPO4. Dark-field STEM image (a) and bright-field STEM image (b) of reduced Co-YPO4 (1.0 wt%) sample, and corresponding elemental maps for O, P, Co, Y (c-f).

Fig. 3. Characterization of Co-YPO4 and YPO4. In situ UV-vis DRS (a) and ex situ XPS (b) of Co-YPO4 (1.0 wt%) catalyst pretreatment at different atmosphere (air, H2, and ethanol). (c) In situ FTIR spectra of CO adsorption on YPO4 and Co-YPO4 (1.0 wt%) catalysts, recorded at -173 °C. (d) 31P MAS NMR spectra of YPO4 and Co-YPO4 (1.0 wt%) catalysts.

Fig. 4. Acid and base characterization of xCo-YPO4 and YPO4. (a) NH3- and (b) CO2-TPD-MS profiles.

Fig. 5. FTIR spectra of pyridine adsorbed on YPO4 and Co-YPO4 (1.0 wt%) catalysts.

Fig. 6. Dependence of product selectivity on the ethanol conversion over Co-YPO4 (a) and YPO4 (b) catalysts. Reaction conditions: 350 °C, C2H5OH/N2 = 5.7/94.3, WHSV = 1-50 gC2H5OH?gCat.-1?h-1, Vtotal = 30 mL?min-1.

Fig. 7. MS signal profiles of ethanol temperature-programmed surface reaction (TPSR) profiles over Co-YPO4 (a) and YPO4 (b) catalysts.

Scheme 1. Proposed reaction pathway for butadiene formation.

Fig. 8. (a) Ethanol conversion and products selectivity as a function of time-on-stream over Co-YPO4. Reaction conditions: 200 mg catalyst mass, T = 350 °C, PC2H5OH = 5.7 kPa, PN2 = 94.3 kPa, Vtotal = 30 mL·min-1. (b,c) Thermogravimetry (TG)-MS profiles of spent Co-YPO4 catalyst under a TPO environment.

参考文献

[1]	J. Sun, Y. Wang, ACS Catal., 2014, 4, 1078-1090.
[2]	E. V. Makshina, M. Dusselier, W. Janssens, J. Degreve, P. A. Jacobs, B. F. Sels, Chem. Soc. Rev., 2014, 43, 7917-7953.
[3]	W. C. White, Chem.-Biol. Interact., 2007, 166, 10-14.
[4]	G. Pomalaza, P. Arango Ponton, M. Capron, F. Dumeignil, Catal. Sci. Technol., 2020, 10, 4860-4911.
[5]	K. Mamedov, R. J. Davis, ACS Catal., 2023, 3333-3344.
[6]	S.-H. Chung, T. Li, T. Shoinkhorova, S. Komaty, A. Ramirez, I. Mukhambetov, E. Abou-Hamad, G. Shterk, S. Telalovic, A. Dikhtiarenko, B. Sirks, P. Lavrik, X. Tang, B. M. Weckhuysen, P. C. A. Bruijnicx, J. Gascon, J. Ruiz-Martinez, Nat. Catal., 2023, 6, 363-376.
[7]	Q.-N. Wang, L. Shi, W. Li, W.-C. Li, R. Si, F. Schüth, A.-H. Lu, Catal. Sci. Technol., 2018, 8, 472-479.
[8]	S.-Q. Cheng, X.-F. Weng, Q.-N. Wang, B.-C. Zhou, W.-C. Li, M.-R. Li, L. He, D.-Q. Wang, A.-H. Lu, Chin. J. Catal., 2021, 43, 1092-1100.
[9]	M. E. Witzke, P. J. Dietrich, M. Y. S. Ibrahim, K. Al-Bardan, M. D. Triezenberg, D. W. Flaherty, Chem. Commun., 2017, 53, 597-600.
[10]	X. Li, J. Pang, Y. Zhao, P. Wu, W. Yu, P. Yan, Y. Su, M. Zheng, Chin. J. Catal., 2023, 49, 91-101.
[11]	F. Xue, C. Miao, Y. Yue, W. Hua, Z. Gao, Green Chem., 2017, 19, 5582-5590.
[12]	J. Sun, K. Zhu, F. Gao, C. Wang, J. Liu, C. H. F. Peden, Y. Wang, J. Am. Chem. Soc., 2011, 133, 11096-11099.
[13]	B. Zhao, Y. Men, A. Zhang, J. Wang, R. He, W. An, S. Li, Appl. Catal. A, 2018, 558, 150-160.
[14]	V. L. Dagle, M. D. Flake, T. L. Lemmon, J. S. Lopez, L. Kovarik, R. A. Dagle, Appl. Catal. B, 2018, 236, 576-587.
[15]	H. Li, J. Pang, N. R. Jaegers, L. Kovarik, M. Engelhard, A. W. Savoy, J. Hu, J. Sun, Y. Wang, J. Energy Chem., 2021, 54, 7-15.
[16]	W. E. Taifan, Y. Li, J. P. Baltrus, L. Zhang, A. I. Frenkel, J. Baltrusaitis, ACS Catal., 2019, 9, 269-285.
[17]	T. De Baerdemaeker, M. Feyen, U. Mueller, B. Yilmaz, F.-S. Xiao, W. Zhang, T. Yokoi, X. Bao, H. Gies, D. E. De Vos, ACS Catal., 2015, 5, 3393-3397.
[18]	T. Yan, W. Dai, G. Wu, S. Lang, M. Hunger, N. Guan, L. Li, ACS Catal., 2018, 8, 2760-2773.
[19]	C. Wang, M. Zheng, X. Li, X. Li, T. Zhang, Green Chem., 2019, 21, 1006-1010.
[20]	V. L. Sushkevich, I. I. Ivanova, Appl. Catal. B, 2017, 215, 36-49.
[21]	Q.-N. Wang, B.-C. Zhou, X.-F. Weng, S.-P. Lv, F. Schüth, A.-H. Lu, Chem. Commun., 2019, 55, 10420-10423.
[22]	B.-C. Zhou, W.-C. Li, W.-L. Lv, S.-Y. Xiang, X.-Q. Gao, A.-H. Lu, ACS Catal., 2022, 12, 12045-12054.
[23]	W.-L. Lv, L. He, W.-C. Li, B.-C. Zhou, S.-P. Lv, A.-H. Lu, Green Chem., 2023, 25, 2653-2662.
[24]	D. Jiang, G. Fang, Y. Tong, X. Wu, Y. Wang, D. Hong, W. Leng, Z. Liang, P. Tu, L. Liu, K. Xu, J. Ni, X. Li, ACS Catal., 2018, 8, 11973-11978.
[25]	B. Lu, S. Ma, S. Liang, Z. Wang, Y. Liu, S. Mao, H. Ban, L. Wang, Y. Wang, ACS Catal., 2023, 13, 4866-4872.
[26]	Q.-N. Wang, X.-F. Weng, B.-C. Zhou, S.-P. Lv, S. Miao, D. Zhang, Y. Han, S. L. Scott, F. Schüth, A.-H. Lu, ACS Catal., 2019, 9, 7204-7216.
[27]	B. C. Zhou, Q. N. Wang, X. F. Weng, L. He, W. C. Li, A. H. Lu, ChemCatChem, 2020, 12, 2341-2347.
[28]	D. Jiang, X. Wu, J. Mao, J. Ni, X. Li, Chem. Commun., 2016, 52, 13749-13752.
[29]	C. Angelici, B. M. Weckhuysen, P. C. A. Bruijnincx, ChemSusChem, 2013, 6, 1595-1614.
[30]	N. M. Eagan, M. D. Kumbhalkar, J. S. Buchanan, J. A. Dumesic, G. W. Huber, Nat. Rev. Chem., 2019, 3, 223-249.
[31]	X. Y. Wu, G. Q. Fang, Y. Q. Tong, D. H. Jiang, Z. Liang, W. H. Leng, L. Liu, P. X. Tu, H. J. Wang, J. Ni, X. N. Li, ChemSusChem, 2018, 11, 71-85.
[32]	J. J. Dai, H. B. Zhang, Sci. China-Mater., 2019, 62, 1642-1654.
[33]	C. Angelici, F. Meirer,A. M. J. Van Der Eerden, H. L. Schaink, A. Goryachev, J. P. Hofmann, E. J. M. Hensen, B. M. Weckhuysen, P. C. A. Bruijnincx, ACS Catal., 2015, 5, 6005-6015.
[34]	W. Dai, S. Zhang, Z. Yu, T. Yan, G. Wu, N. Guan, L. Li, ACS Catal., 2017, 7, 3703-3706.
[35]	L. Qi, Y. Zhang, M. A. Conrad, C. K. Russell, J. Miller, A. T. Bell, J. Am. Chem. Soc., 2020, 142, 14674-14687.
[36]	K. Wang, W. Gao, F. Chen, G. Liu, J. Wu, N. Liu, Y. Kawabata, X. Guo, Y. He, P. Zhang, G. Yang, N. Tsubaki, Appl. Catal. B, 2022, 301, 120822.
[37]	R. Otomo, C. Yamaguchi, D. Iwaisako, S. Oyamada, Y. Kamiya, ACS Sustainable Chem. Eng., 2019, 7, 3027-3033.
[38]	G. Innocenti, E. Papadopoulos, G. Fornasari, F. Cavani, A. J. Medford, C. Sievers, ACS Catal., 2020, 10, 11936-11950.
[39]	H. Zhou, L. Chen, Y. Guo, X. Liu, X.-P. Wu, X.-Q. Gong, Y. Wang, ACS Catal., 2022, 4806-4812.
[40]	H. Yan, M. Zhao, X. Feng, S. Zhao, X. Zhou, S. Li, M. Zha, F. Meng, X. Chen, Y. Liu, D. Chen, N. Yan, C. Yang, Angew. Chem. Int. Ed., 2022, 61, e202116059.
[41]	H. Gong, X. Zhao, Y. Qin, W. Xu, X. Wei, Q. Peng, Y. Ma, S. Dai, P. An, Z. Hou, J. Catal., 2022, 408, 245-260.
[42]	M. Chen, J. Xia, H. Li, X. Zhao, Q. Peng, J. Wang, H. Gong, S. Dai, P. An, H. Wang, Z. Hou, ChemCatChem, 2021, 13, 3801-3814.
[43]	M. J. Cordon, J. Zhang, S. C. Purdy, E. C. Wegener, K. A. Unocic, L. F. Allard, M. Zhou, R. S. Assary, J. T. Miller, T. R. Krause, F. Lin, H. Wang, A. J. Kropf, C. Yang, D. Liu, Z. Li, ACS Catal., 2021, 11, 7193-7209.
[44]	J. Zhang, E. C. Wegener, N. R. Samad, J. W. Harris, K. A. Unocic, L. F. Allard, S. Purdy, S. Adhikari, M. J. Cordon, J. T. Miller, T. R. Krause, S. Cheng, D. Liu, M. Li, X. Jiang, Z. Wu, Z. Li, ACS Catal., 2021, 11, 9885-9897.
[45]	M. J. Cordon, J. Zhang, N. R. Samad, J. W. Harris, K. A. Unocic, M. Li, D. Liu, Z. Li, ACS Sustainable Chem. Eng., 2022, 10, 5702-5707.
[46]	Q. Zhu, L. Yin, K. Ji, C. Li, B. Wang, T. Tan, ACS Sustainable Chem. Eng., 2020, 8, 1555-1565.
[47]	W. O. Milligan, D. F. Mullica, G. W. Beall, L. A. Boatner, Inorg. Chim. Acta, 1982, 60, 39-43.
[48]	Z.-P. Hu, G. Qin, J. Han, W. Zhang, N. Wang, Y. Zheng, Q. Jiang, T. Ji, Z.-Y. Yuan, J. Xiao, Y. Wei, Z. Liu, J. Am. Chem. Soc., 2022, 144, 12127-12137.
[49]	Y. Gao, L. Peng, J. Long, Y. Wu, Y. Dai, Y. Yang, Microporous Mesoporous Mater., 2021, 323, 111187.
[50]	Y. Dai, J. Gu, S. Tian, Y. Wu, J. Chen, F. Li, Y. Du, L. Peng, W. Ding, Y. Yang, J. Catal., 2020, 381, 482-492.
[51]	Z. Huang, D. He, W. Deng, G. Jin, K. Li, Y. Luo, Nat. Commun., 2023, 14, 100.
[52]	T. Yan, L. Yang, W. Dai, C. Wang, G. Wu, N. Guan, M. Hunger, L. Li, J. Catal., 2018, 367, 7-15.

Co-YPO₄双功能催化剂促进乙醇高值转化制丁二烯

PO₄^3- coordinated Co²⁺ species on yttrium phosphate boosting the valorization of ethanol to butadiene

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 9

参考文献

相关文章 15

编辑推荐

Metrics

[1]	王哲, 王春鹏, 陆冰, 陈志荣, 王勇, 毛善俊. 界面电子扰动促进的C-H键活化[J]. 催化学报, 2024, 56(1): 130-138.
[2]	孙嘉辰, 陈赛, 付东龙, 王伟, 王显辉, 孙国栋, 裴春雷, 赵志坚, 巩金龙. 氧扩散与表面反应在VO_x-Ce_1‒_xZr_xO₂催化丙烷脱氢反应中的影响[J]. 催化学报, 2023, 52(9): 217-227.
[3]	周双龙, 赵亮, 吕征, 代钰, 张琦, 赖建平, 王磊. 局部氧自由基的性质促进电催化乙醇选择性生成CO₂[J]. 催化学报, 2023, 52(9): 154-163.
[4]	Abhishek R. Varma, Bhushan S. Shrirame, Sunil K. Maity, Deepti Agrawal, Naglis Malys, Leonardo Rios-Solis, Gopalakrishnan Kumar, Vinod Kumar. C4二醇的发酵生产及其化学催化升级为高价值化学品的研究进展[J]. 催化学报, 2023, 52(9): 99-126.
[5]	周波, 石建巧, 姜一民, 肖磊, 逯宇轩, 董帆, 陈晨, 王特华, 王双印, 邹雨芹. 强化脱氢动力学实现超低电池电压和大电流密度下抗坏血酸电氧化[J]. 催化学报, 2023, 50(7): 372-380.
[6]	李显泉, 庞纪峰, 赵于嘉, 吴鹏飞, 于文广, 颜佩芳, 苏扬, 郑明远. Cu-MFI催化剂上Cu^δ⁺催化乙醇脱氢制乙醛[J]. 催化学报, 2023, 49(6): 91-101.
[7]	邢亚楠, 康磊磊, 马静远, 蒋齐可, 苏杨, 张盛鑫, 徐晓燕, 李林, 王爱琴, 刘智攀, 马思聪, 刘晓艳, 张涛. Sn₁Pt单原子合金催化剂在丙烷脱氢反应中的应用[J]. 催化学报, 2023, 48(5): 164-174.
[8]	张龙康, 马跃, 刘昌呈, 万志鹏, 翟承伟, 王新, 徐浩, 关业军, 吴鹏. 脱金属-还原策略诱导创制高分散PtZn合金催化剂用于丙烷脱氢反应[J]. 催化学报, 2023, 55(12): 241-252.
[9]	田昊, 徐冰君. 六方氮化硼催化的乙烷丙烷共脱氢: 一种C-H键活化和机理研究的有效手段[J]. 催化学报, 2022, 43(8): 2173-2182.
[10]	王慧宁, 关安翔, 张俊波, 米玉莹, 李思, 袁涛涛, 静超, 张丽娟, 张林娟, 郑耿锋. 铜掺杂的羟基氧化镍用于高效电催化乙醇氧化[J]. 催化学报, 2022, 43(6): 1478-1484.
[11]	王梦茹, 王奕, 牟效玲, 林荣和, 丁云杰. 1,3-丁二烯选择性加氢催化剂的设计策略以及构效关系[J]. 催化学报, 2022, 43(4): 1017-1041.
[12]	程世群, 翁雪霏, 王庆楠, 周百川, 李文翠, 李名润, 贺雷, 王东琪, 陆安慧. 富缺陷BN负载的高分散Cu催化乙醇脱氢制乙醛[J]. 催化学报, 2022, 43(4): 1092-1100.
[13]	王彩琴, Danil Bukhvalov, M. Cynthia Goh, 杜玉扣, 杨小飞. 分级结构AgAu纳米合金用于高效电催化乙醇氧化[J]. 催化学报, 2022, 43(3): 851-861.
[14]	陈锦杨, 吴红谕, 桂清文, 晏山舒, 邓婕, 林英武, 曹忠, 何卫民. 电催化4-喹诺酮和二烃基二硒醚的交叉脱氢偶联反应[J]. 催化学报, 2021, 42(9): 1445-1450.
[15]	邵方君, 姚子豪, 高怡静, 周强, 包志康, 庄桂林, 钟兴, 伍川, 魏中哲, 王建国. 双功能催化剂Ru₂P在N-杂环加氢和无受体脱氢反应中的几何效应和电子效应[J]. 催化学报, 2021, 42(7): 1185-1194.