Direction esterification of bio-based succinate catalyzed by solid super acid SO42-/ZrO2

doi:10.16085/j.issn.1000-6613.2022-2139

Abstract

Abstract:

The preparation of succinic acid by biological fermentation instead of petroleum-based method has attracted wide attention because of its cheap raw materials and low environmental impact. However, most product by biological fermentation is succinate. Therefore, it is often necessary to acidify succinate with inorganic acid. With CH₃OH and CO₂ as esterification reagents, disodium succinate can be directly esterified to dimethyl succinate without using of inorganic acid, and the generated carbonate can be used to fix carbon dioxide and adjust the pH of biological fermentation broth. Herein, this paper systematically investigated the catalytic performance of different molecular sieves for this reaction and explored their deactivation reasons. Due to the easy deactivation and low acid content of molecular sieves, solid superacid SO₄^2-/ZrO₂ was used to improve the reaction. X-ray diffractometer, specific surface area and porosity analyzer, thermal gravimetric analyzer, X-ray photoelectron spectroscopy, temperature programmed chemisorption instrument were used to investigate the effects of calcining temperature and concentration of dipping solution on the direct esterification of disodium succinate catalyzed by SO₄^2-/ZrO₂ to prepare dimethyl succinate, and the cycle stability of the catalyst. The results showed that under the preparation conditions of H₂SO₄ concentration of 2mol/L and calcination temperature of 550℃, the prepared SO₄^2-/ZrO₂ catalyst had excellent catalytic activity, and the yield and selectivity of dimethyl succinate were 89.25% and 93.56%, respectively. In addition, the catalyst remained high catalytic activity after being used for five times without any treatments, indicating its good stability.

Key words: catalyst, carbon dioxide, esterification, reactivity

摘要：

生物发酵法制备丁二酸因制备原料廉价易得、制备工艺对环境影响较小等优点，在替代石油基原料生产丁二酸方面受到广泛关注，但生物发酵生产的丁二酸主要以丁二酸盐形式存在。因此，常需要使用无机酸将丁二酸盐进行酸化处理。以CH₃OH和CO₂为酯化试剂，可实现丁二酸二钠的直接酯化，获取丁二酸二甲酯，有效地避免了无机酸的使用，且生成的碳酸盐既可固定二氧化碳，也可用于生物发酵液pH的调节。本文在此基础上系统考察了不同分子筛对此反应的催化效果，针对分子筛容易失活和酸量较低的缺点，将分子筛替换为固体超强酸SO₄^2-/ZrO₂，对该反应体系进行进一步改进。采用X射线衍射仪、比表面积及孔隙度分析仪、热重分析仪、X射线光电子能谱仪、程序升温化学吸附仪等探究了焙烧温度和浸渍液浓度对SO₄^2-/ZrO₂催化丁二酸二钠直接酯化制备丁二酸二甲酯的影响以及催化剂循环稳定性，结果表明在H₂SO₄浸渍浓度为2mol/L和焙烧温度为550℃的制备条件下所得SO₄^2-/ZrO₂催化剂具有较优的催化活性，丁二酸二甲酯的收率和选择性分别为89.25%和93.56%，此外，催化剂不经处理连续使用5次依旧维持较高催化活性，表明其具有较好的稳定性。

关键词: 催化剂, 二氧化碳, 酯化, 活性

CLC Number:

TQ920.9

YIN Keke, WANG Yugao, GU Bao, SHEN Jun. Direction esterification of bio-based succinate catalyzed by solid super acid SO₄^2-/ZrO₂[J]. Chemical Industry and Engineering Progress, 2023, 42(10): 5213-5222.

尹科科, 王玉高, 谷豹, 申峻. 固体超强酸SO₄^2-/ZrO₂催化生物基丁二酸盐直接酯化[J]. 化工进展, 2023, 42(10): 5213-5222.

Figures/Tables 19

References 42

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类型	Si/Al	比表面积/m²∙g^-1	孔径/nm
MCM-41	全硅	≥1000	4
USY	5	≥805	3.8
SAPO-34	0.25	≥550	0.4
HY	≥2.7	≥650	0.74

类型	Si/Al	比表面积/m²∙g^-1	孔径/nm
MCM-41	全硅	≥1000	4
USY	5	≥805	3.8
SAPO-34	0.25	≥550	0.4
HY	≥2.7	≥650	0.74

浸渍浓度/mol·L^-1	C	O	S	Zr
0.5	15.92	56.63	5.83	21.62
1	16.73	56.53	6.12	20.61
2	26.33	49.93	6.47	17.27
3	18.58	56.08	8.86	16.48

浸渍浓度/mol·L^-1	C	O	S	Zr
0.5	15.92	56.63	5.83	21.62
1	16.73	56.53	6.12	20.61
2	26.33	49.93	6.47	17.27
3	18.58	56.08	8.86	16.48

浸渍浓度/mol·L^-1	比表面积/m²·g^-1	孔径/nm	孔容/cm³·g^-1
2	86.83	7.93	0.17
3	60.43	7.08	0.11

Direction esterification of bio-based succinate catalyzed by solid super acid SO₄^2-/ZrO₂

固体超强酸SO₄^2-/ZrO₂催化生物基丁二酸盐直接酯化

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Figures/Tables 19

References 42

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样品	C	O	S	Zr
SZ-未使用	26.33	49.93	6.47	17.27
SZ-使用后	27.73	50.08	2.69	19.5

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