固体超强酸SO42-/ZrO2催化生物基丁二酸盐直接酯化

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

摘要/Abstract

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

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

中图分类号:

TQ920.9

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.

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.

图/表 19

图1 SZ催化DSA酯化反应实验操作流程

图2 分子筛种类对DSA酯化的产物收率和选择性的影响（反应温度160℃、反应时间2h、CO2初始压力1MPa、DSA初始添加量1mmol、催化剂添加量0.2g）

表1 实验中涉及的几种分子筛的参数

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

图3 HY分子筛稳定性评价

图4 HY反应前后的NH3-TPD曲线

图5 不同焙烧温度所得SZ对催化活性的影响（反应温度160℃、反应时间2h、CO2初始压力1MPa、DSA初始添加量1mmol、催化剂添加量0.2g、浸渍浓度为2mol/L）

图6 不同焙烧温度所得SZ的XRD谱图

图7 550℃焙烧所得SZ的TG和DTG曲线

图8 不同H2SO4浸渍浓度所得SZ对催化活性的影响（反应温度160℃、反应时间2h、CO2初始压力1MPa、DSA初始添加量1mmol、催化剂添加量0.2g，焙烧温度550℃）

表2 不同H2SO4浸渍浓度所得SZ表面组分的元素组成（物质的量分数）

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

图9 不同H2SO4浸渍浓度所得SZ的XPS谱图

图10 不同H2SO4浸渍浓度所得SZ的XRD谱图

图11 不同H2SO4浸渍浓度所得SZ的N2物理吸附分析

表3 不同H2SO4浸渍浓度所得SZ的比表面积、孔径和孔容

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

图12 550℃焙烧、2mol/L硫酸浸渍所得SZ的FTIR谱图

图13 反应条件对DSA直接酯化的影响[(a)的反应条件为：反应温度160℃、反应时间2h、CO2初始压力1MPa、DSA初始添加量1mmol；(b)的反应条件为：反应温度160℃、CO2初始压力1MPa、DSA初始添加量1mmol、催化剂添加量0.2g；(c)的反应条件为：反应时间8h、CO2初始压力1MPa、DSA初始添加量1mmol、催化剂添加量0.2g]

图14 SZ的稳定性测试（反应温度160℃、反应时间8h、CO2初始压力1MPa、DSA初始添加量1mmol、催化剂添加量0.2g）

图15 SZ反应前后NH3-TPD分析

表4 反应前后SZ表面组分的元素组成（物质的量分数）

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

参考文献 42

1	张耀, 邱晓曼, 陈程鹏, 等. 生物法制造丁二酸研究进展[J]. 化工学报, 2020, 71(5): 1964-1975.
	ZHANG Yao, QIU Xiaoman, CHEN Chengpeng, et al. Recent progress in microbial production of succinic acid[J]. CIESC Journal, 2020, 71(5): 1964-1975.
2	HE Liangtu, LIU Lei, HUANG Yuzhang, et al. One-pot synthesis of dimethyl succinate from d-fructose using Amberlyst-70 catalyst[J]. Molecular Catalysis, 2021, 508: 111584.
3	夏榆, 姚勇波, 姚菊明, 等. PBS/天然高分子复合材料的现状及进展[J]. 塑料, 2022, 51(2): 85-88, 100.
	XIA Yu, YAO Yongbo, YAO Juming, et al. Current status and development of PBS/natural polymer composite[J]. Plastics, 2022, 51(2): 85-88, 100.
4	李求进, 梁伯润. 聚乙二醇丁二酸酯/酚醛树脂共混物的结晶行为[J]. 合成技术及应用, 2006, 21(1): 1-3.
	LI Qiujin, LIANG Borun. Study on crystallization behavior of PESu/phenolic blends[J]. Synthetic Technology and Application, 2006, 21(1): 1-3.
5	WAN Xinyan, REN Dezhang, LIU Yunjie, et al. Facile synthesis of dimethyl succinate via esterification of succinic anhydride over ZnO in methanol[J]. ACS Sustainable Chemistry and Engineering, 2018, 6(3): 2969-2975.
6	姚伶俐, 潘海峰, 田文娟, 等. 代谢工程改造大肠杆菌合成丁二酸及发酵罐放大工艺[J]. 微生物学通报, 2018, 45(12): 2541-2551.
	YAO Lingli, PAN Haifeng, TIAN Wenjuan, et al. Production of succinate by a metabolic engineered Escherichia coli and its scale-up process in fermentor[J]. Microbiology China, 2018, 45(12): 2541-2551.
7	OKINO Shohei, NOBURYU Ryoji, SUDA Masako, et al. An efficient succinic acid production process in a metabolically engineered Corynebacterium glutamicum strain[J]. Applied Microbiology and Biotechnology, 2008, 81(3): 459-464.
8	SONG Hyohak, LEE Sang Yup. Production of succinic acid by bacterial fermentation[J]. Enzyme and Microbial Technology, 2006, 39(3): 352-361.
9	ORJUELA Alvaro, YANEZ Abraham J, PEEREBOOM Lars, et al. A novel process for recovery of fermentation-derived succinic acid[J]. Separation and Purification Technology, 2011, 83: 31-37.
10	ORJUELA Alvaro, KOLAH Aspi, HONG Xi, et al. Diethyl succinate synthesis by reactive distillation[J]. Separation and Purification Technology, 2012, 88: 151-162.
11	CABRERA-RODRÍGUEZ Carlos I, VAN DER WIELEN Luuk A M, STRAATHOF Adrie J J. Separation and catalysis of carboxylates: Byproduct reduction during the alkylation with dimethyl carbonate[J]. Industrial & Engineering Chemistry Research, 2015, 54(44): 10964-10973.
12	LÓPEZ-GARZÓN Camilo S, OTTENS Marcel, VAN DER WIELEN Luuk A M, et al. Direct downstream catalysis: From succinate to its diethyl ester without intermediate acidification[J]. Chemical Engineering Journal, 2012, 200/201/202: 637-644.
13	LÓPEZ-GARZÓN Camilo S, VAN DER WIELEN Luuk A M, STRAATHOF Adrie J J. Green upgrading of succinate using dimethyl carbonate for a better integration with fermentative production[J]. Chemical Engineering Journal, 2014, 235: 52-60.
14	LÃ³PEZ-GARZÃ³N Camilo S, VAN DER WIELEN Luuk A M, STRAATHOF Adrie J J. Ester production from bio-based dicarboxylates via direct downstream catalysis: Succinate and 2, 5-furandicarboxylate dimethyl esters[J]. RSC Advances, 2016, 6(5): 3823-3829.
15	CABRERA-RODRÃGUEZ Carlos I, PALTRINIERI Laura, DE SMET Louis C P M, et al. Recovery and esterification of aqueous carboxylates by using CO₂-expanded alcohols with anion exchange[J]. Green Chemistry, 2017, 19(3): 729-738.
16	BARVE Prashant P, KAMBLE Sanjay P, JOSHI Jyeshtharaj B, et al. Preparation of pure methyl esters from corresponding alkali metal salts of carboxylic acids using carbon dioxide and methanol[J]. Industrial & Engineering Chemistry Research, 2012, 51(4): 1498-1505.
17	谷豹. 丁二酸钠直接酯化及固体酸催化酯化制备丁二酸二甲酯[D]. 太原: 太原理工大学, 2022.
	GU Bao. Preparation of dimethyl succinate by direct esterification of sodium succinate and esterification catalyzed by solid acid[D]. Taiyuan: Taiyuan University of Technology, 2022.
18	薛淼, 朱美华, 钟彩君, 等. ZSM-5分子筛膜在乙酸异戊酯酯化反应中的应用[J]. 膜科学与技术, 2018, 38(4): 107-112.
	XUE Miao, ZHU Meihua, ZHONG Caijun, et al. Application of ZSM-5 zeolite membrane for esterification of isoamyl acetate[J]. Membrane Science and Technology, 2018, 38(4): 107-112.
19	李三喜, 徐妍如, 王松. SO₄ ^2-/TiO₂-HZSM-5固体超强酸催化剂的制备及酯化性能[J]. 化工进展, 2015, 34(3): 745-750.
	LI Sanxi, XU Yanru, WANG Song. Preparation of solid superacid SO₄ ^2-/TiO₂-HZSM-5 catalyst and its catalytic performance in esterification[J]. Chemical Industry and Engineering Progress, 2015, 34(3): 745-750.
20	WANG Shan, PU Jianglong, WU Jiaqin, et al. SO₄ ^2-/ZrO₂ as a solid acid for the esterification of palmitic acid with methanol: Effects of the calcination time and recycle method[J]. ACS Omega, 2020, 5(46): 30139-30147.
21	WANG Anqi, WANG Junxia, WANG Hui, et al. Synthesis of SO₄ ^2-/TiO₂-ZnAl₂O₄ composite solid acids as the esterification catalysts[J]. RSC Advances, 2017, 7(23): 14224-14232.
22	WANG Pengzhao, YUE Yuanyuan, WANG Tinghai, et al. Alkane isomerization over sulfated zirconia solid acid system[J]. International Journal of Energy Research, 2020, 44(5): 3270-3294.
23	IGLESIAS Jose, MELERO Juan A, MORALES Gabriel, et al. Dehydration of xylose to furfural in alcohol media in the presence of solid acid catalysts[J]. ChemCatChem, 2016, 8(12): 2089-2099.
24	THIMMARAJU N, MOHAMED SHAMSHUDDIN S Z, PRATAP S R, et al. Effective synthesis of novel O-acetylated compounds over ZrO₂-Al₂O₃ solid acid[J]. Arabian Journal of Chemistry, 2019, 12(8): 1860-1869.
25	胡亚飞, 蔡晶, 李小森. 环戊烷-甲烷水合物生成过程的温度特性[J]. 化工进展, 2016, 35(5): 1418-1427.
	HU Yafei, CAI Jing, LI Xiaosen. System temperature properties in the process of the cyclopentane-methane binary hydrates formation[J]. Chemical Industry and Engineering Progress, 2016, 35(5): 1418-1427.
26	赵培瑞, 李娜, 陈茜文, 等. 改性固体酸SO₄ ^2-/ZrO₂催化合成没食子酸甲酯的研究[J]. 中南林业科技大学学报, 2017, 37(6): 114-118.
	ZHAO Peirui, LI Na, CHEN Qianwen, et al. Study on synthesis of methyl gallate catalyzed by modified solid superacid SO₄ ^2-/ZrO₂ [J]. Journal of Central South University of Forestry & Technology, 2017, 37(6): 114-118.
27	张萍, 李露, 于凤丽, 等. SO₄ ^2-/ZrO₂的制备工艺对催化橡胶籽油裂解油酯化的影响[J]. 燃料化学学报, 2013, 41(11): 1322-1327.
	ZHANG Ping, LI Lu, YU Fengli, et al. Preparation of SO₄ ^2-/ZrO₂ catalyst and its performance in the esterification of pyrolytic rubber seed oil[J]. Journal of Fuel Chemistry and Technology, 2013, 41(11): 1322-1327.
28	ZHANG Hongwei, YANG Weijia, ROSLAN Irwan Iskandar, et al. A combo Zr-HY and Al-HY zeolite catalysts for the one-pot cascade transformation of biomass-derived furfural to γ-valerolactone[J]. Journal of Catalysis, 2019, 375: 56-67.
29	SONG Hua, CUI Xuehan, JIANG Bolong, et al. Preparation of SO₄ ^2-/ZrO₂ solid superacid and oxidative desulfurization using K₂FeO₄ [J].Research on Chemical Intermediates, 2015, 41(1): 365-382.
30	WARD D A, KO E I. One-step synthesis and characterization of zirconia-sulfate aerogels as solid superacids[J]. Journal of Catalysis, 1994, 150(1): 18-33.
31	张亚平, 黎汉生, 甄彬, 等. SO₄ ^2-/TiO₂-SiO₂固体超强酸的制备、表征及其性能[J]. 化工进展, 2011, 30(S1): 155-158.
	ZHANG Yaping, LI Hansheng, ZHEN Bin, et al. Preparation, characterization and catalytic properties of SO₄ ^2-/TiO₂-SiO₂ solid superacid[J]. Chemical Industry and Engineering Progress, 2011, 30(S1): 155-158.
32	ARDIZZONE S, BIANCHI C L, GRASSI E. The role of the oxide precursor on the features of sulphated zirconia[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 1998, 135(1/2/3): 41-51.
33	KUMARI Latha, LI W Z, XU J M, et al. Controlled hydrothermal synthesis of zirconium oxide nanostructures and their optical properties[J]. Crystal Growth & Design, 2009, 9(9): 3874-3880.
34	BEDILO Alexander F, KIM Vladimir I, VOLODIN Alexander M. Effect of light on reactions over sulfated zirconia[J]. Journal of Catalysis, 1998, 176(2): 294-304.
35	WANG Anqi, WANG Junxia, LU Can, et al. Esterification for biofuel synthesis over an eco-friendly and efficient kaolinite-supported SO₄ ^2-/ZnAl₂O₄ macroporous solid acid catalyst[J]. Fuel, 2018, 234: 430-440.
36	马惠琴, 王卫, 马媛媛. La改性固体超强酸S₂O₈ ^2-/ZrO₂-Al₂O₃的制备及催化性能研究[J]. 材料导报, 2014, 28(6): 48-52, 64.
	MA Huiqin, WANG Wei, MA Yuanyuan. Preparation and catalytic properties study of solid superacid catalyst S₂O₈ ^2-/ZrO₂-Al₂O₃ modified by lanthanum[J]. Materials Review, 2014, 28(6): 48-52, 64.
37	金顶峰, 王新庆, 金红晓, 等. 硫酸化介孔氧化锆固体超强酸的制备和应用研究[J]. 材料工程, 2008, 36(10): 223-227.
	JIN Dingfeng, WANG Xinqing, JIN Hongxiao, et al. Synthesis and performance of sulfated mesoporous zorcina solid superacid[J]. Journal of Materials Engineering, 2008, 36(10): 223-227.
38	赵燕, 郑琦宏, 于洁. SO₄ ^2-/TiO₂型光催化材料的制备与表征[J]. 材料导报, 2015, 29(S1): 313-315, 322.
	ZHAO Yan, ZHENG Qihong, YU Jie. Preparation and characterization of SO₄ ^2-/TiO₂ photocatalyst[J]. Materials Review, 2015, 29(S1): 313-315, 322.
39	戎梅竹, 申延明, 刘宏伟, 等. SO₄ ^2-/ZrO₂固体超强酸的制备及表征[J]. 化工科技, 2006, 14(4): 34-37.
	RONG Meizhu, SHEN Yanming, LIU Hongwei, et al. Preparation and characterization of superacid SO₄ ^2-/ZrO₂ [J]. Science & Technology in Chemical Industry, 2006, 14(4): 34-37.
40	郑云天, 位艳宾, 徐庆茹, 等. SO₄ ^2-/ZrO₂固体超强酸的制备及催化性能[J]. 化工技术与开发, 2016, 45(7): 7-10.
	ZHENG Yuntian, WEI Yanbin, XU Qingru, et al. Preparation and catalytic properties of SO₄ ^2-/ZrO₂ solid superacid[J]. Technology & Development of Chemical Industry, 2016, 45(7): 7-10.
41	王晋东, 李文志, 杜志杰, 等. Ni-S₂O₈ ^2-/TiO₂固体超强酸催化解聚木质素的研究[J]. 太阳能学报, 2017, 38(4): 867-873.
	WANG Jindong, LI Wenzhi, DU Zhi jie, et al. Study of lignin catalytic depolymerization by solid superacid Ni-S₂O₈ ^2-/TiO₂ [J]. Acta Energiae Solaris Sinica, 2017, 38(4): 867-873.
42	SHI Xuejun, WU Yulong, LI Panpan, et al. Catalytic conversion of xylose to furfural over the solid acid SO₄ ^2-/ZrO₂-Al₂O₃/SBA-15 catalysts[J]. Carbohydrate Research, 2011, 346(4): 480-487.

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固体超强酸SO₄^2-/ZrO₂催化生物基丁二酸盐直接酯化

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

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