甲醇和乙酸甲酯一步法制丙酸甲酯催化剂的可控制备与性能调控

doi:10.11949/0438-1157.20250156

摘要/Abstract

摘要：

丙酸甲酯（MP）作为医药、香料合成等领域的关键有机中间体，其现有生产工艺面临分离能耗高、生产效率低等挑战。基于此，本研究提出一种以甲醇与乙酸甲酯为原料，在原料高分压（60 kPa）条件下在固定床反应器内连续合成MP的新路线。通过Ti改性策略构筑了一系列高性能Ti-Cs/SiO₂催化剂，并采用XRD、BET、TEM、XPS、CO₂/NH₃-TPD和UV-Vis测试对其物理化学特性进行了表征。结果表明，Ti的引入显著调节了催化剂的酸碱特性，弱酸占总酸位点与弱碱占总碱位点比例对羟醛缩合反应活性有重要影响。在一步法制MP的关键步骤（甲醛和乙酸甲酯羟醛缩合反应）中，乙酸甲酯的转化率随Ti的负载量呈火山型趋势变化，当Ti的负载量为4%（质量分数）时，转化率最高（29.4%）。相应地，在甲醇和乙酸甲酯一步法制MP的串联反应中，该催化剂表现出最高的催化活性，MP的收率达23.6%。本研究揭示了Ti改性对催化剂酸碱特性及反应性能的影响机制，为甲醇和乙酸甲酯一步法合成MP的催化剂设计及工艺放大提供了理论依据和技术支撑。

关键词: 羟醛缩合, 串联催化, 酸碱调控, 催化剂, 丙酸甲酯, 多相反应, 合成

Abstract:

Methyl propionate (MP), as a key organic intermediate in pharmaceutical and fragrance synthesis, currently faces production challenges including high energy consumption during separation and low production efficiency. Based on this, this study proposes a new route for continuous synthesis of MP in a fixed bed reactor using methanol and methyl acetate as raw materials under high partial pressure (60 kPa) of raw materials. A series of high-performance Ti-modified Cs/SiO₂ catalysts were developed, and their physicochemical properties were characterized using XRD, BET, TEM, XPS, CO₂/NH₃-TPD and UV-Vis spectroscopy. The results indicate that the introduction of Ti significantly modulates the acid-base properties of the catalyst, and the proportion of weak acid sites to total acid sites coupled with the ratio of weak base sites to total base sites critically governs the activity in aldol condensation reactions. In the key step of the one-step MP synthesis (aldol condensation of formaldehyde and methyl acetate), the conversion of methyl acetate exhibited a volcano-shaped trend with the loading of Ti, reaching a maximum of 29.4% at a Ti loading of 4%(mass). Correspondingly, in the tandem reaction of methanol and methyl acetate to produce MP, the catalyst demonstrated the highest catalytic activity, with an MP yield of 23.6%. This study elucidates the mechanism by which Ti modification affects the acid-base properties and reaction performance of the catalysts, providing theoretical insights and technical support for the catalyst design and process scale-up of one-step MP synthesis from methanol and methyl acetate.

Key words: aldol condensation, tandem catalysis, acid-base regulation, catalyst, methyl propionate, multiphase reaction, synthesis

中图分类号:

TQ 032.4

巢欣旖, 陈文尧, 张晶, 钱刚, 周兴贵, 段学志. 甲醇和乙酸甲酯一步法制丙酸甲酯催化剂的可控制备与性能调控[J]. 化工学报, 2025, 76(8): 4030-4041.

Xinyi CHAO, Wenyao CHEN, Jing ZHANG, Gang QIAN, Xinggui ZHOU, Xuezhi DUAN. Controlled preparation and performance regulation of catalysts for one-step synthesis of methyl propionate from methanol and methyl acetate[J]. CIESC Journal, 2025, 76(8): 4030-4041.

图/表 11

图1 催化剂性能评价装置与流程示意图

Fig.1 Schematic diagram of the catalyst performance evaluation apparatus and process

图2 催化剂的元素分布和形貌分析

Fig.2 Elemental distribution and morphological analysis of the catalysts

图3 载体和催化剂的N2等温吸脱附曲线和孔径分布曲线

Fig.3 N2 adsorption-desorption isotherms and pore size distribution curves of the support and supported catalysts

表1 载体和负载型催化剂的孔结构参数

Table 1 Pore structure parameters of the support and supported catalysts

催化剂	比表面积/(m²/g)	孔容/(cm³/g)	平均孔径/nm
SiO₂	428.9	0.76	6.71
Cs/SiO₂	92.0	0.59	21.85
1Ti-Cs/SiO₂	235.9	0.84	11.48
2Ti-Cs/SiO₂	240.9	0.75	9.65
3Ti-Cs/SiO₂	241.5	0.65	8.62
4Ti-Cs/SiO₂	246.1	0.64	8.42
5Ti-Cs/SiO₂	269.3	0.70	8.19

图4 催化剂的XPS谱图

Fig.4 XPS spectra of catalysts

表2 催化剂中的Ti3+、Ti4+和Olatt的比例

Table 2 Ratios of Ti3+， Ti4+ and Olatt in the catalysts

催化剂	Ti³⁺/Ti	Ti⁴⁺/Ti	O^latt/O
Cs/SiO₂	—	—	14.2%
1Ti-Cs/SiO₂	32.18%	67.82%	14.4%
2Ti-Cs/SiO₂	36.60%	63.40%	16.4%
3Ti-Cs/SiO₂	40.78%	59.22%	17.0%
4Ti-Cs/SiO₂	47.06%	52.94%	17.3%
5Ti-Cs/SiO₂	50.52%	49.48%	17.6%

图5 xTi-Cs/SiO2的紫外吸收光谱

Fig.5 UV-Vis absorption spectra of xTi-Cs/SiO₂ catalysts

图6 催化剂的NH3-TPD曲线和CO2-TPD曲线

Fig.6 NH₃-TPD and CO₂-TPD profiles of the catalysts

表3 催化剂的酸碱性质

Table 3 Acid-base properties of catalysts

催化剂	总酸量/ (μmol/g)	不同强度酸量/(μmol/g)			总碱量/ (μmol/g)	不同强度碱量/(μmol/g)
催化剂	总酸量/ (μmol/g)	弱	中强	强	总碱量/ (μmol/g)	弱	中强	强
1Ti-Cs/SiO₂	87	36	37	15	188	90	60	36
2Ti-Cs/SiO₂	101	43	40	17	164	84	59	22
3Ti-Cs/SiO₂	115	52	48	15	142	77	47	19
4Ti-Cs/SiO₂	130	64	51	16	123	73	37	13
5Ti-Cs/SiO₂	134	72	51	11	110	72	35	3

图7 xTi-Cs/SiO2催化剂的固定床评价结果以及酸碱位点比例与羟醛缩合性能的关系

Fig.7 Catalytic performance of xTi-Cs/SiO2 catalysts in fixed-bed reactor and correlation between weak acid/base site proportion and aldol condensation performance

图8 4Ti-Cs/SiO2催化剂在一步法制MP反应中的稳定性与再生性能

Fig.8 Cyclic stability and regenerability of 4Ti-Cs/SiO2 catalyst in one-step synthesis of MP from methanol/methyl acetate

参考文献 48

[1]	Zhou X P, Dong J C, Zhao Y, et al. Synergy of photo- and photothermal-catalytic synthesis of methyl propionate from ethylene and carbon dioxide over B–TiO₂/Ru[J]. ACS Sustainable Chemistry & Engineering, 2023, 11(24): 9255-9263.
[2]	Wang L M, Zhang G L, Zhao H, et al. Encapsulation of phosphine-palladium complex in USY zeolite for hydroesterification of ethylene to methyl propionate[J]. Chemical Engineering Science, 2025, 304: 120976.
[3]	王鲁明, 李增喜. 丙酸甲酯催化合成过程研究进展[J]. 工程研究——跨学科视野中的工程, 2024, 16(5): 481-499.
	Wang L M, Li Z X. Research progress on the catalytic synthesis process of methyl propionate[J]. Journal of Engineering Studies, 2024, 16(5): 481-499.
[4]	Sun T, Wang G, Guo X P, et al. A highly active NiMoAl catalyst prepared by a solvothermal method for the hydrogenation of methyl acrylate[J]. Catalysts, 2022, 12(10): 1118.
[5]	Liu G L, Li G, Song H Y. Direct synthesis of methyl propionate from n-propyl alcohol and methanol using gold catalysts[J]. Catalysis Letters, 2009, 128(3): 493-501.
[6]	Zhang B, Yuan H Y, Liu Y, et al. Ambient-pressure alkoxycarbonylation for sustainable synthesis of ester[J]. Nature Communications, 2024, 15(1): 7837.
[7]	Sivakumar G, Kumar R, Yadav V, et al. Multi-functionality of methanol in sustainable catalysis: beyond methanol economy[J]. ACS Catalysis, 2023, 13(22): 15013-15053.
[8]	Chen W Y, Zuo J, Sang K, et al. Leveraging the proximity and distribution of Cu-Cs sites for direct conversion of methanol to esters/aldehydes[J]. Angewandte Chemie (International Ed), 2024, 63(1): e202314288.
[9]	Guan Y N, Ma H Q, Chen W Y, et al. Methyl methacrylate synthesis: thermodynamic analysis for oxidative esterification of methacrolein and aldol condensation of methyl acetate[J]. Industrial & Engineering Chemistry Research, 2020, 59(39): 17408-17416.
[10]	左骥, 罗莉, 谢永锴, 等. 甲醇无氧脱氢制甲醛Cu催化剂的粒径效应[J]. 化工进展, 2025, 44(3): 1347-1354.
	Zuo J, Luo L, Xie Y K, et al. Effect of Cu catalyst particle size on methanol nonoxidative dehydrogenation to formaldehyde[J]. Chemical Industry and Engineering Progress, 2025, 44(3): 1347-1354.
[11]	Wang G, Li Z X, Li C S. Recent progress in one-step synthesis of acrylic acid and methyl acrylate via aldol reaction: catalyst, mechanism, kinetics and separation[J]. Chemical Engineering Science, 2022, 247: 117052.
[12]	Feng X Z, Sun B, Yao Y, et al. Renewable production of acrylic acid and its derivative: new insights into the aldol condensation route over the vanadium phosphorus oxides[J]. Journal of Catalysis, 2014, 314: 132-141.
[13]	Wang Y M, Wang Z L, Hao X, et al. Nb-doped vanadium phosphorus oxide catalyst for the aldol condensation of acetic acid with formaldehyde to acrylic acid[J]. Industrial & Engineering Chemistry Research, 2018, 57(36): 12055-12060.
[14]	He T, Qu Y X, Wang J D. Aldol condensation reaction of methyl acetate and formaldehyde over cesium oxide supported on silica gel: an experimental and theoretical study[J]. Catalysis Letters, 2019, 149(2): 373-389.
[15]	Ai M. Formation of methyl methacrylate by condensation of methyl propionate with formaldehyde over silica-supported cesium hydroxide catalysts[J]. Applied Catalysis A: General, 2005, 288(1/2): 211-215.
[16]	Tai J R, Davis R J. Synthesis of methacrylic acid by aldol condensation of propionic acid with formaldehyde over acid-base bifunctional catalysts[J]. Catalysis Today, 2007, 123(1/2/3/4): 42-49.
[17]	Wang Y N, Yan R Y, Lv Z P, et al. Lanthanum and cesium-loaded SBA-15 catalysts for MMA synthesis by aldol condensation of methyl propionate and formaldehyde[J]. Catalysis Letters, 2016, 146(9): 1808-1818.
[18]	Xu L, Wang X P, Song J H, et al. Acid promoter-modified Cs/Al₂O₃ catalyst for methyl methacrylate production by aldol condensation of methyl propionate with formaldehyde[J]. Industrial & Engineering Chemistry Research, 2023, 62(49): 21130-21139.
[19]	Sararuk C, Yang D, Zhang G L, et al. One-step aldol condensation of ethyl acetate with formaldehyde over Ce and P modified cesium supported alumina catalyst[J]. Journal of Industrial and Engineering Chemistry, 2017, 46: 342-349.
[20]	Wu Z Y, Wang L M, Li Z X, et al. Unveiling the promotion of Brønsted acid sites in Cs dispersion and consequential Si-O-Cs species formation for methyl acrylate synthesis from methyl acetate and formaldehyde over Cs/Beta zeolite catalyst[J]. Chemical Engineering Journal, 2023, 474: 145655.
[21]	Guo Z J, Zhang G L, Wang L, et al. Fe-modified Cs–P/γ-Al₂O₃ catalyst for synthesis of methyl methacrylate from methyl propionate and formaldehyde[J]. Industrial & Engineering Chemistry Research, 2020, 59(8): 3334-3341.
[22]	Deng S L, Yan T T, Ran R, et al. Influence of Al oxides on Cs-SiO₂ catalysts for vapor phase aldol condensation of methyl acetate and formaldehyde[J]. Industrial & Engineering Chemistry Research, 2022, 61(17): 5766-5777.
[23]	Bao Q, Qi H, Zhang C L, et al. Highly catalytic activity of Ba/γ-Ti-Al₂O₃ catalyst for aldol condensation of methyl acetate with formaldehyde[J]. Catalysis Letters, 2018, 148(11): 3402-3412.
[24]	Rekoske J E, Barteau M A. Kinetics, selectivity, and deactivation in the aldol condensation of acetaldehyde on anatase titanium dioxide[J]. Industrial & Engineering Chemistry Research, 2011, 50(1): 41-51.
[25]	Zhang Z Y, Berdugo-Díaz C E, Bregante D T, et al. Aldol condensation and esterification over Ti-substituted *BEA zeolite: mechanisms and effects of pore hydrophobicity[J]. ACS Catalysis, 2022, 12(2): 1481-1496.
[26]	Idriss H, Kim K S, Barteau M A. Carbon-Carbon bond formation via aldolization of acetaldehyde on single crystal and polycrystalline TiO₂ surfaces[J]. Journal of Catalysis, 1993, 139(1): 119-133.
[27]	Gao B Z, Zhu Q R, Yi Y H, et al. Catalytic performance of amorphous Ti/SiO₂ in the gas-phase epoxidation of propylene with H₂O₂ [J]. European Journal of Inorganic Chemistry, 2023, 26(22): e202200661.
[28]	Guo Y J, Hwang S J, Katz A. Hydrothermally robust Ti/SiO₂ epoxidation catalysts via surface modification with oligomeric PMHS[J]. Molecular Catalysis, 2019, 477: 110509.
[29]	Liu J Y, Li Z X, Bian Y H, et al. Promotional effect of Ti on catalytic performance of Cs/Ti-SiO₂ for conversion of methyl propionate and formaldehyde to methyl methacrylate[J]. Chemical Engineering Science, 2024, 283: 119441.
[30]	Pham T N, Shi D C, Sooknoi T, et al. Aqueous-phase ketonization of acetic acid over Ru/TiO₂/carbon catalysts[J]. Journal of Catalysis, 2012, 295: 169-178.
[31]	Jia B Y, Wu M J, Zhang H, et al. Ti functionalized hierarchical-pore UiO-66(Zr/Ti) catalyst for the transesterification of phenyl acetate and dimethyl carbonate[J]. New Journal of Chemistry, 2019, 43(43): 16981-16989.
[32]	Arillo M A, López M L, Pico C, et al. Surface characterisation of spinels with Ti(Ⅳ) distributed in tetrahedral and octahedral sites[J]. Journal of Alloys and Compounds, 2001, 317: 160-163.
[33]	Biesinger M C, Lau L W M, Gerson A R, et al. Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn[J]. Applied Surface Science, 2010, 257(3): 887-898.
[34]	Lin Y L, Wang T J, Jin Y. Surface characteristics of hydrous silica-coated TiO₂ particles[J]. Powder Technology, 2002, 123(2/3): 194-198.
[35]	Hong Z, Zhao G Q, Huang F T, et al. Enhancing the side-chain alkylation of toluene with methanol to styrene over the Cs-modified X zeolite by the assistance of basic picoline as a co-catalyst[J]. Green Energy & Environment, 2022, 7(6): 1241-1252.
[36]	Li Q, Deng S L, Liu J Y, et al. PEG-assisted synthesis of highly dispersed Cs/Zr-SiO₂ catalyst for aldol condensation of methyl acetate with formaldehyde[J]. Chemical Engineering Science, 2025, 301: 120716.
[37]	Shintaku H, Nakajima K, Kitano M, et al. Lewis acid catalysis of TiO₄ tetrahedra on mesoporous silica in water[J]. ACS Catalysis, 2014, 4(4): 1198-1204.
[38]	Liang X H, Peng X X, Xia C J, et al. Improving Ti incorporation into the BEA framework by employing ethoxylated chlorotitanate as Ti precursor: postsynthesis, characterization, and incorporation mechanism[J]. Industrial & Engineering Chemistry Research, 2021, 60(3): 1219-1230.
[39]	Guidotti M, Ravasio N, Psaro R, et al. Epoxidation on titanium-containing silicates: do structural features really affect the catalytic performance?[J]. Journal of Catalysis, 2003, 214(2): 242-250.
[40]	Li W Q, Qiu M H, Li W T, et al. Au supported defect free TS-1 for enhanced performance of gas phase propylene epoxidation with H₂ and O2[J]. Sustainable Energy & Fuels, 2022, 6(10): 2462-2470.
[41]	Hu J, Lu Z P, Yin H B, et al. Aldol condensation of acetic acid with formaldehyde to acrylic acid over SiO₂-, SBA-15-, and HZSM-5-supported V-P-O catalysts[J]. Journal of Industrial and Engineering Chemistry, 2016, 40: 145-151.
[42]	Yan T T, Deng S L, Ran R, et al. Cesium loaded on an Al-modified silica support catalyst for methyl acrylate synthesis by aldol condensation of methyl acetate and formaldehyde[J]. Industrial & Engineering Chemistry Research, 2022, 61(7): 2748-2758.
[43]	Wang B, Deng S L, Bian Y H, et al. Aldol condensation of methyl propionate and formaldehyde: thermodynamics, reaction process, and network[J]. Industrial & Engineering Chemistry Research, 2022: acs.iecr.2c02570.
[44]	Zuo C C, Li C S, Ge T T, et al. Spherical P-modified catalysts for heterogeneous cross-aldol condensation of formaldehyde with methyl acetate for methyl acrylate production[J]. The Canadian Journal of Chemical Engineering, 2017, 95(11): 2104-2111.
[45]	Ma H Q, Guan Y N, Chen W Y, et al. Support effects of Cs/Al₂O₃ catalyzed aldol condensation of methyl acetate with formaldehyde[J]. Catalysis Today, 2021, 365: 310-317.
[46]	李晓云, 孙彦民, 于海斌. 甲醇催化脱氢制无水甲醛研究进展[C]//全国工业催化信息站, 工业催化杂志社.第七届全国工业催化技术及应用年会论文集. 天津: 中国海油天津化工研究设计院催化技术重点实验室, 2010: 134-136.
	Li X Y, Sun Y M, Yu H B. Research progress in catalytic dehydrogenation of methanol to anhydrous formaldehyde[C]// National Industrial Catalysis Information Station, Industrial Catalysis Journal. Proceedings of the 7th National Annual Conference on Industrial Catalytic Technology and Applications. Tianjin: CNOOC Tianjin Chemical Research & Design Institute Key Laboratory of Catalytic Technology, 2010: 134-136.
[47]	Ran R, Zhu W, Zhang G L, et al. Unraveling the coking and deactivation behavior of Al-Cs/SiO₂ catalyst in the aldol condensation of methyl propionate with formaldehyde[J]. Industrial & Engineering Chemistry Research, 2024, 63(3): 1286-1297.
[48]	Xu L, Wang X P, Song J H, et al. Coking and deactivation behavior study of Ce-modified Cs-Nb/Al₂O₃ in aldol condensation of methyl propionate with formaldehyde[J]. Molecular Catalysis, 2024, 564: 114323.