Relationship between the Acid-base Properties of Nitrogen-modified ZnO-ZrO2/SBA-15 Catalysts and Their Catalytic Performance in the Synthesis of 1,3-Butadiene from Ethanol

doi:10.6023/A23100474

Abstract

1,3-Butadiene (hereinafter referred to as butadiene), as an important organic intermediate in the chemical industry, has a wide range of uses in the petroleum and rubber industries. Using ethanol as raw material to produce butadiene can solve the non-renewable problem of raw materials, so it has received more and more attention. In this paper, catalysts were hydrothermally synthesized by using SBA-15 as the support, nitrate as the oxide precursor, and nitrogen-containing organic compounds as the additive. And then, the relationship between catalytic performance (ethanol conversion and butadiene yield) and the acid-base properties of catalysts was explored in the synthesis of butadiene from ethanol. Specifically, we used melamine (M), cyanuric acid (Ma), 1,10-phenanthroline (Pm), imidazole (Im), and 1,3,5-triazine (St) as nitrogen-containing additives for the preparation of Zn-Zr/SBA-15＋X catalysts. Through the activity evaluation of the catalysts, the activities of ethanol dehydrogenation and dehydration, acetaldehyde condensation, and Meerwein-Ponndorf-Verley (MPV) reactions were calculated. Then, by analyzing the dependence of these activities and butadiene yield on the acidity and basicity (the strength and number of acidic/basic sites) of catalysts, we found that appropriate amounts of weak acid (0.022 mmol·g⁻¹), moderate acid (0.078 mmol·g⁻¹), moderate base (0.055 mmol·g⁻¹), and strong base (0.056 mmol·g⁻¹) are helpful for the ethanol dehydrogenation, whereas excess amount of weak acid and moderate acid will lead to the ethanol dehydration. Appropriate amounts of moderate acid (0.078 mmol·g⁻¹) and moderate base (0.055 mmol·g⁻¹) will favor the acetaldehyde condensation and MPV reactions. The butadiene yield is closely related to the activities of acetaldehyde condensation and MPV. The melamine-modified catalyst (Zn-Zr/SBA-15＋M) has the optimum amounts of weak acid, moderate acid, moderate base, and strong base in accordance with the above quantities, resulting in the best catalytic performance: 99.5% conversion of ethanol, 65.5% selectivity of butadiene, and 0.45 g_BD·g_cat⁻¹·h⁻¹ of butadiene productivity.

Key words: nitrogen modification, ZnO-ZrO₂, acid-base property, ethanol, butadiene

Cite this article

Bing Xue, Weixin Guan, Peng Wang, Shaowen Hou, Xinhui Chen, Yixing Wang, Huanqi Gou, Fenghao Guo, Mengchuang Wang, Tianzi Wang, Jinde Liu, Zhou Zheng, Shougen Chai, Jiarui Chen, Jianlin Zhang, Yunfei Ji, Jun Ni. Relationship between the Acid-base Properties of Nitrogen-modified ZnO-ZrO₂/SBA-15 Catalysts and Their Catalytic Performance in the Synthesis of 1,3-Butadiene from Ethanol[J]. Acta Chimica Sinica, 2024, 82(5): 493-502.

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Fig. & Tab. 16

Figure 1. The reaction mechanism of synthesizing butadiene from ethanol

催化剂^a	转化率/%	选择性/%						丁二烯收率/%	产能^c/ (g_BD·g_cat⁻¹·h⁻¹)
催化剂^a	转化率/%	丁二烯	乙烯	乙醛	乙醚	丁醇	其他^b	丁二烯收率/%	产能^c/ (g_BD·g_cat⁻¹·h⁻¹)
Zn-Zr/SBA-15	90.9	50.0	4.72	9.73	0.79	2.90	31.9	45.5	0.32
Zn-Zr/SBA-15＋M	99.5	65.5	8.42	5.47	0.54	1.07	18.9	65.2	0.45
Zn-Zr/SBA-15＋Ma	98.5	63.7	10.4	4.84	0.63	0.96	19.5	62.7	0.44
Zn-Zr/SBA-15＋Pm	99.4	61.4	13.2	2.60	0.63	0.96	21.2	61.0	0.42
Zn-Zr/SBA-15＋Im	96.8	60.7	13.5	3.81	0.62	0.90	20.5	58.8	0.41
Zn-Zr/SBA-15＋St	97.1	59.8	12.5	4.55	0.63	1.00	21.5	58.1	0.40

Table 1. Catalytic performance of Zn-Zr/SBA-15＋X catalysts

催化剂	关键反应步骤活性/%
催化剂	脱氢^a	脱水^b	缩合^c	MPV^d
Zn-Zr/SBA-15	94.49	5.51	54.50	50.00
Zn-Zr/SBA-15＋M	90.94	8.96	67.53	65.50
Zn-Zr/SBA-15＋Ma	88.97	11.03	65.38	63.70
Zn-Zr/SBA-15＋Pm	86.17	13.83	62.96	61.40
Zn-Zr/SBA-15＋Im	85.88	14.12	62.30	60.70
Zn-Zr/SBA-15＋St	86.87	13.13	61.51	59.80

Table 2. The activity of key steps in the process of ethanol to butadiene

催化剂	比表面积^a/ (m²·g⁻¹)	孔容^b/ (cm³·g⁻¹)	平均孔径^c/ nm
Zn-Zr/SBA-15	385.1	0.94	0.95
Zn-Zr/SBA-15＋M	346.6	1.02	1.17
Zn-Zr/SBA-15＋Ma	360.7	1.02	1.04
Zn-Zr/SBA-15＋Pm	354.4	0.95	1.05
Zn-Zr/SBA-15＋Im	361.4	1.00	1.07
Zn-Zr/SBA-15＋St	351.1	0.96	1.07

Table 3. Textural properties of Zn-Zr/SBA-15＋X catalysts

Figure 2. XRD patterns of Zn-Zr/SBA-15＋X catalysts (a) Zn-Zr/SBA-15; (b) Zn-Zr/SBA-15＋M; (c) Zn-Zr/SBA-15＋Ma; (d) Zn-Zr/SBA-15＋Pm; (e) Zn-Zr/SBA-15＋Im; (f) Zn-Zr/SBA-15＋St

Catalyst	Acid sites concentration^a/ (mmol·g⁻¹), [T^c/℃]			Basic sites concentration^b/ (mmol·g⁻¹), [T^c/℃]
Catalyst	Weak	Moderate	Total	Weak	Moderate	Strong	Total
Zn-Zr/SBA-15	0.026 [181]	0.070 [368]	0.096	0.001 [102]	0.052 [323]	0.052 [400]	0.105
Zn-Zr/SBA-15＋M	0.022 [181]	0.078 [320]	0.100	0.0008 [98]	0.055 [347]	0.056 [400]	0.112
Zn-Zr/SBA-15＋Ma	0.030 [184]	0.091 [348]	0.121	0.0006 [105]	0.054 [331]	0.058 [400]	0.113
Zn-Zr/SBA-15＋Pm	0.028 [187]	0.089 [360]	0.117	0.0009 [103]	0.058 [375]	0.063 [400]	0.122
Zn-Zr/SBA-15＋Im	0.027 [179]	0.115 [345]	0.142	0.0009 [95]	0.056 [367]	0.060 [400]	0.117
Zn-Zr/SBA-15＋St	0.029 [191]	0.086 [368]	0.115	0.0012 [116]	0.061 [362]	0.052 [400]	0.114

Table 4. The acidity and basicity of Zn-Zr/SBA-15＋X catalysts

Figure 3. FTIR spectra of pyridine adsorption over Zn-Zr/SBA-15 catalyst: (A) at different temperatures; (B) at room temperature

Figure 4. FTIR spectra of pyridine adsorption over Zn-Zr/SBA-15＋M catalyst: (A) at different temperatures; (B) at room temperature

Figure 5. FTIR spectra of pyridine adsorption over Zn-Zr/SBA-15＋Ma catalyst: (A) at different temperatures; (B) at room temperature

Figure 6. FTIR spectra of pyridine adsorption over Zn-Zr/SBA-15＋Pm catalyst: (A) at different temperatures; (B) at room temperature

Figure 7. FTIR spectra of pyridine adsorption over Zn-Zr/SBA-15＋Im catalyst: (A) at different temperatures; (B) at room temperature

Figure 8. FTIR spectra of pyridine adsorption over Zn-Zr/SBA-15＋St catalyst: (A) at different temperatures; (B) at room temperature

Figure 9. The dehydrogenation ability against (a) the amount of weak acid; (b) the amount of moderate acid; (c) the strength of moderate acid; (d) the amount of weak base; (e) the amount of moderate base; (f) the strength of moderate base; (g) the amount of strong base; (h) the amount of total acid; (i) the amount of total base

Figure 10. The condensation ability against (a) the amount of weak acid; (b) the amount of moderate acid; (c) the strength of moderate acid; (d) the amount of weak base; (e) the amount of moderate base; (f) the strength of moderate base; (g) the amount of strong base; (h) the amount of total acid; (i) the amount of total base

Figure 11. The MPV ability against (a) the amount of weak acid; (b) the amount of moderate acid; (c) the strength of moderate acid; (d) the amount of weak base; (e) the amount of moderate base; (f) the strength of moderate base; (g) the amount of strong base; (h) the amount of total acid; (i) the amount of total base

Figure 12. The BD yield against (a) the amount of weak acid; (b) the amount of moderate acid; (c) the strength of moderate acid; (d) the amount of weak base; (e) the amount of moderate base; (f) the strength of moderate base; (g) the amount of strong base; (h) the amount of total acid; (i) the amount of total base

References 15

[1]	Corson, B. B.; Stahly, E. E.; Jones, H. E.; Bishop, H. D. Ind. Eng. Chem. 1949, 41, 1012.
[2]	Bruijnincx, P. C. A.; Weckhuysen, B. M. Angew. Chem., Int. Ed. 2013, 52, 11980. doi: 10.1002/anie.201305058 pmid: 24136811
[3]	(a) Cespi, D.; Passarini, F.; Vassura, I.; Cavani, F. Green Chem. 2016, 18, 1625.
	(b) Shylesh, S.; Gokhale, A. A.; Scown, C. D.; Kim, D.; Ho, C. R.; Bell, A. T. ChemSusChem 2016, 9, 1462.
[4]	Pomalaza, G.; Arango Ponton, P.; Capron, M.; Dumeignil, F. Catal. Sci. Technol. 2020, 10, 4860.
[5]	(a) Li, H.; Riisager, A.; Saravanamurugan, S.; Pandey, A.; Sangwan, R. S.; Yang, S.; Luque, R. ACS Catal. 2018, 8, 148.
	(b) Bin Samsudin, I.; Zhang, H.; Jaenicke, S.; Chuah, G.-K. Chem. Asian J. 2020, 15, 4199.
[6]	Sushkevich, V. L.; Ivanova, I. I.; Ordomsky, V. V.; Taarning, E. ChemSusChem 2014, 7, 2527. doi: 10.1002/cssc.201402346 pmid: 25123990
[7]	Makshina, E. V.; Janssens, W.; Sels, B. F.; Jacobs, P. A. Catal. Today 2012, 198, 338.
[8]	Zhou, B.-X.; Ding, S.-S.; Zhang, B.-J.; Xu, L.; Chen, R.-S.; Luo, L.; Huang, W.-Q.; Xie, Z.; Pan, A.; Huang, G.-F. Appl. Catal., B 2019, 254, 321.
[9]	Osuga, R.; Fang, P.; Nishiyama, H.; Takizawa, K.; Yagihashi, N.; Yokoi, T.; Kondo, J. N. Microporous Mesoporous Mater. 2022, 346, 112278.
[10]	Tu, P.-X.; Xue, B.; Tong, Y.-Q.; Zhou, J.; He, Y.-H.; Cheng, Y.-H.; Ni, J.; Li, X.-N. ChemistrySelect 2020, 5, 7258.
[11]	Damyanova, S.; Grange, P.; Delmon, B. J. Catal. 1997, 168, 421.
[12]	(a) Larina, O. V.; Kyriienko, P. I.; Balakin, D. Y.; Vorokhta, M.; Khalakhan, I.; Nychiporuk, Y. M.; Matolín, V.; Soloviev, S. O.; Orlyk, S. M. Catal. Sci. Technol. 2019, 9, 3964. doi: 10.1039/c9cy00991d
	(b) Connell, G.; Dumesic, J. A. J. Catal. 1987, 105, 285.
	(c) Larina, O. V.; Kyriienko, P. I.; Soloviev, S. O. Catal. Lett. 2015, 145, 1162.
[13]	Ordomsky, V. V.; Sushkevich, V. L.; Ivanova, I. I. J. Mol. Catal. A: Chem. 2010, 333, 85.
[14]	(a) Jiang, D.-H.; Fang, G.-Q.; Tong, Y.-Q.; Wu, X.-Y.; Wang, Y.-F.; Hong, D.-S.; Leng, W.-H.; Liang, Z.; Tu, P.-X.; Liu, L.; Xu, K.-Y.; Ni, J.; Li, X.-N. ACS Catal. 2018, 8, 11973.
	(b) Wu, X.-Y.; Fang, G.-Q.; Liang, Z.; Leng, W.-H.; Xu, K.-Y.; Jiang, D.-H.; Ni, J.; Li, X.-N. Catal. Commun. 2017, 100, 15.
[15]	(a) Urbano, F. J.; Aramendía, M. A.; Marinas, A.; Marinas, J. M.. J. Catal. 2009, 268, 79.
	(b) Liang, Z.; Jiang, D.-H.; Fang, G.-Q.; Leng, W.-H.; Tu, P.-X.; Tong, Y.-Q.; Liu, L.; Ni, J.; Li, X.-N. ChemistrySelect 2019, 4, 4364. doi: 10.1002/slct.201900712

氮改性ZnO-ZrO₂/SBA-15催化剂的酸碱性与其催化乙醇合成1,3-丁二烯反应性能的关系

Relationship between the Acid-base Properties of Nitrogen-modified ZnO-ZrO₂/SBA-15 Catalysts and Their Catalytic Performance in the Synthesis of 1,3-Butadiene from Ethanol

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氮改性ZnO-ZrO2/SBA-15催化剂的酸碱性与其催化乙醇合成1,3-丁二烯反应性能的关系