NaY分子筛Lewis酸促进甲醇经亚硝酸甲酯分解制二甲氧基甲烷※

doi:10.6023/A21120619

化学学报 ›› 2022, Vol. 80 ›› Issue (4): 438-443.DOI: 10.6023/A21120619 上一篇下一篇

所属专题：中国科学院青年创新促进会合辑

研究通讯

NaY分子筛Lewis酸促进甲醇经亚硝酸甲酯分解制二甲氧基甲烷^※

江辉波^a^,^b, 林姗姗^a^,^b, 徐玉平^b, 孙径^b, 徐忠宁^b^,^*(), 郭国聪^b^,^*()

a 福州大学石油化工学院福州 350116
b 中国科学院福建物质结构研究所结构化学国家重点实验室福州 350002

投稿日期:2021-12-31 发布日期:2022-04-28
通讯作者: 徐忠宁, 郭国聪
作者简介:
^※ 庆祝中国科学院青年创新促进会十年华诞.
基金资助:
国家重点研发计划项目(2021YFB3801604); 国家重点研发计划项目(2017YFA0206802); 国家重点研发计划项目(2017YFA0700103); 国家重点研发计划项目(2018YFA0704500); 国家自然科学基金委员会面上项目(22172171)

Lewis Acid in NaY Zeolite High Selectively Catalyze Methanol to Dimethoxymethane via Methyl Nitrite^※

Huibo Jiang^a^,^b, Shanshan Lin^a^,^b, Yuping Xu^b, Jing Sun^b, Zhongning Xu^b(), Guocong Guo^b()

a College of Chemical Engineering, Fuzhou University, Fuzhou 350116, China
b State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China

Received:2021-12-31 Published:2022-04-28
Contact: Zhongning Xu, Guocong Guo
About author:
^※ Dedicated to the 10th anniversary of the Youth Innovation Promotion Association, CAS.
Supported by:
National Key Research and Development Program of China(2021YFB3801604); National Key Research and Development Program of China(2017YFA0206802); National Key Research and Development Program of China(2017YFA0700103); National Key Research and Development Program of China(2018YFA0704500); General Program of National Natural Science Foundation of China(22172171)

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1. Supporting Information-A21120619.pdf(420KB)

摘要/Abstract

二甲氧基甲烷(Dimethoxymethane, DMM)作为一种基础有机化学品, 在树脂、溶剂、燃料等领域具有广泛用途. 传统合成方法采用甲醇甲醛缩合, 反应效率比较低. 亚硝酸甲酯(CH₃ONO)是一种性质活泼的气体, 可由甲醇、O₂、NO在无需催化剂的条件下获得, 其反应活性比甲醇高很多. 通过亚硝酸甲酯在常压条件下催化分解可以高效制备DMM. 本工作系统研究了不同类型分子筛的酸性对亚硝酸甲酯催化分解制备DMM的影响规律, 催化活性顺序为: NaY (97%)=HY (97%)>HZSM-5 (90%)>Hβ (89%)>NaZSM-5 (18%)>Naβ (6%), DMM选择性顺序为: NaY (53%)>HY (12%)=Naβ (12%)>NaZSM-5 (7%)>Hβ (4%)>HZSM-5 (3%), 其中NaY分子筛是一种性能优异的亚硝酸甲酯分解制备DMM的催化剂. 通过X射线衍射(XRD)、比表面及孔隙度分析(BET)、扫描电子显微镜(SEM)、吡啶红外(Py-FTIR)等结构表征手段, 发现分子筛的酸性位点是促进亚硝酸甲酯分解的活性中心, 而Na⁺和Al物种的Lewis酸是高选择性生成DMM的关键. 本工作可为DMM提供一种新的高效合成路线.

关键词: 亚硝酸甲酯, 二甲氧基甲烷, 分子筛, NaY, Lewis酸

Dimethoxymethane (DMM) has wide application in resin, solvent, and fuel fields as a fundamental organic chemical. The traditional route to synthesize DMM using methanol and formaldehyde as reactants via condensation reaction has poor efficiency. Methyl nitrite (MN), which is obtained by the reaction of methanol, oxygen and nitrite monoxide without catalysts, could be used as raw material to produce DMM through catalytic decomposition. The current work systematically investigated the catalytic activity and selectivity to DMM of several molecular sieves in MN decomposition reaction. The results show that the activity trend is NaY (97%)=HY (97%)>HZSM-5 (90%)>Hβ (89%)>NaZSM-5 (18%)>Naβ (6%), and the DMM selectivity trend is NaY (53%)>HY (12%)=Naβ (12%)>NaZSM-5 (7%)>Hβ (4%)>HZSM-5 (3%). X-ray diffraction (XRD), Brunner-Emmet-Teller measurements (BET), scanning electron microscope (SEM) and Pyridine-IR (Py-IR) experiments have been employed to reveal the structure-activity relationship of these molecular sieves. Combining the temperature-programmed desorption of CO₂ experiments (CO₂-TPD) data with the evaluation results of the catalytic performance of the zeolite catalyst, the basic sites of the zeolite have no direct connection to the catalytic MN decomposition process. Meanwhile, the calcination temperature experiment of NH₄-zeolite and the catalytic performance test experiment of NaY-tetraethoxysilane (TEOS) further proved that the acid site played an essential role in promoting the decomposition of MN, and the results show that the Lewis acidity sites of Na⁺ and low-coordinated Al metal center are key factors to catalyze MN to DMM high selectively. We have proposed the MN decomposition mechanism. In the process of MN decomposition, there are both proton generation and proton consumption processes. Intermediates in the decomposition process are easily protonated by Brönsted acid sites to form by-products. The Lewis acid site of zeolite is generally a low-coordinated Al metal center, which can effectively adsorb and stabilize the oxygen-containing intermediates generated during the decomposition of MN, especially the methoxy and formaldehyde intermediates involved in the production of DMM, which is very beneficial to

the decomposition of MN to DMM. We believe that the research in this paper can provide a new and efficient synthetic route for DMM.

Key words: methyl nitrite, dimethoxymethane, zeolite, NaY, Lewis acid

引用此文

江辉波, 林姗姗, 徐玉平, 孙径, 徐忠宁, 郭国聪. NaY分子筛Lewis酸促进甲醇经亚硝酸甲酯分解制二甲氧基甲烷^※[J]. 化学学报, 2022, 80(4): 438-443.

Huibo Jiang, Shanshan Lin, Yuping Xu, Jing Sun, Zhongning Xu, Guocong Guo. Lewis Acid in NaY Zeolite High Selectively Catalyze Methanol to Dimethoxymethane via Methyl Nitrite^※[J]. Acta Chimica Sinica, 2022, 80(4): 438-443.

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图/表 9

图1. 分子筛(a) HY, (b) HZSM-5, (c) Hβ和(d) NaY的XRD谱图

Figure 1. XRD patterns of zeolites (a) HY, (b) HZSM-5, (c) Hβ and (d) NaY

Sample	S_BET^a/ (m²•g^-1)	V_mic^b/ (cm³•g^-1)	V_mes^c/ (cm³•g^-1)	Average D_p^d/ nm
NaY	918.05	0.32	0.05	4.81
HY	866.37	0.30	0.05	5.73
HZSM-5	324.36	0.10	0.04	6.05
Hβ	594.81	0.17	0.29	9.15

表1. 分子筛的结构性质

Table 1. Structural properties of the zeolites

图2. 200 ℃真空处理观察到的Py-IR光谱: (a) HY, HZSM-5, Hβ; (b) NaY, NaZSM-5, Naβ

Figure 2. Py-IR spectra observed by vacuum treatment at 200 ℃: (a) HY, HZSM-5, Hβ; (b) NaY, NaZSM-5, Naβ

Sample	Conversion/%	Selectivity/%
Sample	Conversion/%	MF	DMM	MeOH
HY	97	69	12	19
HZSM-5	90	79	3	18
Hβ	89	80	4	16
NaY	97	29	53	18
NaZSM-5	18	45	7	48
Naβ	6	25	12	63

表2. 不同分子筛对MN分解反应的催化性能

Table 2. The catalytic performance of different zeolites for the reaction of methyl nitrite decomposition

Sample	Lewis acid sites/ (μmol•g^-1)	Brönsted acid sites/ (μmol•g^-1)
HY	71.4	210.0
HZSM-5	10.7	183.9
Hβ	81.6	111.2
NaY	437.9	8.7
NaZSM-5	102.4	11.3
Naβ	71.6	7.1

表3. 200 ℃条件下Py-IR光谱测定的分子筛酸度

Table 3. Acidity of the zeolites determined by Py-IR spectra at 200 ℃

图3. NH4-β-T的催化性能(T为煅烧温度), 反应条件: 催化剂150 mg, 重量空速(WHSV)=1146 L•kgcat.-1•h-1, 130 ℃, 0.1 MPa

Figure 3. The catalytic performance of NH4-β-T (T is the calcination temperature), reaction condition: 150 mg catalyst, weight hour space velocity (WHSV)=1146 L•kgcat.-1•h-1, 130 ℃, 0.1 MPa

Sample	Conversion/%	Selectivity/%
Sample	Conversion/%	MF	DMM
HY	97	69	12
NaY	97	29	53
NaY-TEOS	96	34	40

表4. HY、NaY 和 NaY-TEOS 的催化性能

Table 4. The catalytic performance of HY, NaY and NaY-TEOS

图4. (a) 分子筛中Brönsted酸活性位点活化MN示意图; (b)分子筛中Lewis酸活性位点活化MN示意图

Figure 4. (a) Schematic diagram of activation of MN at the active site of Brönsted acid in zeolite; (b) schematic diagram of MN activation by Lewis acid active site in zeolite

图5. 亚硝酸甲酯可能的分解路线

Figure 5. Possible decomposition routes of methyl nitrite

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NaY分子筛Lewis酸促进甲醇经亚硝酸甲酯分解制二甲氧基甲烷^※

Lewis Acid in NaY Zeolite High Selectively Catalyze Methanol to Dimethoxymethane via Methyl Nitrite^※

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NaY分子筛Lewis酸促进甲醇经亚硝酸甲酯分解制二甲氧基甲烷※

Lewis Acid in NaY Zeolite High Selectively Catalyze Methanol to Dimethoxymethane via Methyl Nitrite※

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NaY分子筛Lewis酸促进甲醇经亚硝酸甲酯分解制二甲氧基甲烷^※

Lewis Acid in NaY Zeolite High Selectively Catalyze Methanol to Dimethoxymethane via Methyl Nitrite^※