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

doi:10.6023/A23100474

摘要/Abstract

1,3-丁二烯(以下简称丁二烯)作为化工的重要有机中间体, 在石油以及橡胶工业有着广泛的用途. 以乙醇为原料生产丁二烯能够解决生产原料不可再生的问题, 所以受到越来越多的关注. 本工作采用SBA-15为载体, 硝酸盐为氧化物前驱体, 含氮有机物为助剂, 通过水热合成法制备了催化剂, 并探究了乙醇合成丁二烯反应过程中, 乙醇转化率、丁二烯收率与催化剂酸碱性的关系. 具体来说, 使用三聚氰胺(M)、三聚氰酸(Ma)、1,10-菲啰啉(Pm)、咪唑(Im)和1,3,5-三嗪(St)为含氮助剂, 制备了Zn-Zr/SBA-15＋X催化剂. 通过对催化剂的活性评价, 计算得到乙醇脱氢和脱水、乙醛缩合、Meerwein-Ponndorf-Verley (MPV)反应的活性. 根据反应活性和丁二烯收率与催化剂酸碱性(酸碱强度和含量)的变化关系, 发现适当数量的弱酸(0.022 mmol·g⁻¹)、中酸(0.078 mmol·g⁻¹)、中碱(0.055 mmol·g⁻¹)和强碱(0.056 mmol·g⁻¹)有助于乙醇脱氢反应的发生, 过量的弱酸和中酸将导致乙醇的脱水反应. 中等数量的中酸(0.078 mmol·g⁻¹)和中碱(0.055 mmol·g⁻¹)有利于乙醛缩合和MPV反应的发生. 丁二烯收率与乙醛缩合活性和MPV活性关联较大. 三聚氰胺改性的催化剂(Zn-Zr/SBA-15＋M)的弱酸、中酸、中碱和强碱含量符合以上的最优数量, 因此催化性能最优异: 乙醇转化率为99.5%, 丁二烯选择性为65.5%, 丁二烯产能达到了0.45 g_BD·g_cat⁻¹·h⁻¹.

关键词: 氮改性, ZnO-ZrO₂, 酸碱性, 乙醇, 丁二烯

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

引用此文

薛冰, 关伟鑫, 王鹏, 侯少文, 陈欣辉, 王奕星, 苟焕其, 郭锋浩, 王梦闯, 王天姿, 刘金德, 郑洲, 柴寿根, 陈家锐, 张建林, 棘云飞, 倪珺. 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[J]. 化学学报, 2024, 82(5): 493-502.

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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图/表 16

图1. 乙醇合成丁二烯的反应机理

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

表1. Zn-Zr/SBA-15＋X催化剂的活性评价

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

表2. 乙醇合成丁二烯关键反应步骤的活性

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

表3. Zn-Zr/SBA-15＋X催化剂的结构性质

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

图2. Zn-Zr/SBA-15＋X催化剂的XRD图

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

表4. Zn-Zr/SBA-15＋X催化剂的酸碱性

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

图3. Zn-Zr/SBA-15催化剂的吡啶红外图: (A) 不同温度; (B) 室温

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

图4. Zn-Zr/SBA-15＋M催化剂的吡啶红外图: (A) 不同温度; (B) 室温

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

图5. Zn-Zr/SBA-15＋Ma催化剂的吡啶红外图: (A) 不同温度; (B) 室温

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

图6. Zn-Zr/SBA-15＋Pm催化剂的吡啶红外图: (A) 不同温度; (B) 室温

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

图7. Zn-Zr/SBA-15＋Im催化剂的吡啶红外图: (A) 不同温度; (B) 室温

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

图8. Zn-Zr/SBA-15＋St催化剂的吡啶红外图: (A) 不同温度; (B) 室温

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

图9. 脱氢活性与催化剂酸碱性的关联: (a)弱酸含量; (b)中酸含量; (c)中酸强度; (d)弱碱含量; (e)中碱含量; (f)中碱强度; (g)强碱含量; (h)总酸含量; (i)总碱含量

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

图10. 缩合活性与催化剂酸碱性的关联: (a)弱酸含量; (b)中酸含量; (c)中酸强度; (d)弱碱含量; (e)中碱含量; (f)中碱强度; (g)强碱含量; (h)总酸含量; (i)总碱含量

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

图11. MPV活性与催化剂酸碱性的关联: (a)弱酸含量; (b)中酸含量; (c)中酸强度; (d)弱碱含量; (e)中碱含量; (f)中碱强度; (g)强碱含量; (h)总酸含量; (i)总碱含量

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

图12. 丁二烯收率与催化剂酸碱性的关联: (a)弱酸含量; (b)中酸含量; (c)中酸强度; (d)弱碱含量; (e)中碱含量; (f)中碱强度; (g)强碱含量; (h)总酸含量; (i)总碱含量

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

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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

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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