Thermodynamics insights into the gas-phase synthesis of glycolide from methyl glycolate

doi:10.1016/j.cjche.2024.12.024

Chinese Journal of Chemical Engineering ›› 2025, Vol. 81 ›› Issue (5): 171-181.DOI: 10.1016/j.cjche.2024.12.024

Previous Articles Next Articles

Thermodynamics insights into the gas-phase synthesis of glycolide from methyl glycolate

Dai Zhang^1,2, Xiaofeng Xu³, Yueqiang Cao^1,2, Wei Li², Jinghong Zhou^1,2,3, Xinggui Zhou^1,2

1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China;
2. School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China;
3. School of Resources and Environmental Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2024-10-29 Revised:2024-12-12 Accepted:2024-12-19 Online:2025-03-13 Published:2025-05-28
Contact: Yueqiang Cao,E-mail:yqcao@ecust.edu.cn;Jinghong Zhou,E-mail:jhzhou@ecust.edu.cn
Supported by:
This work was financially supported by the National Natural Science Foundation of China (22478106, 22178102, and 22332003), Shanghai Rising-Star Program (23QA1401900), Young Elite Scientists Sponsorship Program by CAST (2023QNRC001), the Open Project of Yunnan Precious Metals Laboratory Co., Ltd (YPML-2023050272).

Thermodynamics insights into the gas-phase synthesis of glycolide from methyl glycolate

Dai Zhang^1,2, Xiaofeng Xu³, Yueqiang Cao^1,2, Wei Li², Jinghong Zhou^1,2,3, Xinggui Zhou^1,2

1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China;
2. School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China;
3. School of Resources and Environmental Engineering, East China University of Science and Technology, Shanghai 200237, China

通讯作者: Yueqiang Cao,E-mail:yqcao@ecust.edu.cn;Jinghong Zhou,E-mail:jhzhou@ecust.edu.cn
基金资助:
This work was financially supported by the National Natural Science Foundation of China (22478106, 22178102, and 22332003), Shanghai Rising-Star Program (23QA1401900), Young Elite Scientists Sponsorship Program by CAST (2023QNRC001), the Open Project of Yunnan Precious Metals Laboratory Co., Ltd (YPML-2023050272).

Abstract

Abstract: Gas-phase synthesis of glycolide (GL) from methyl glycolate (MG) is of great significance for producing biodegradable polyglycolic acid. Here, we report a detailed thermodynamics study for the gas-phase synthesis of GL from MG, which involves complex reaction pathways, by utilizing the Gibbs free energy minimization method. The results indicate that the decompositions of MG and GL and the polymerization of MG are thermodynamically favorable as compared with the target pathway, i.e., the cyclization of MG. Effects of the reaction conditions including temperature, pressure and feed composition on the formation of GL and linear polymers have also been addressed, which demonstrate that the higher temperature and lower pressure can effectively inhibit the formation of linear methyl ester dimer and improve the selectivity to GL. In addition, the higher N₂/MG ratio is beneficial for the formation of GL in the process promoted by catalysts. These thermodynamics results indicate that the process promoted by catalysts would benefit from the kinetics control by high-performance catalysts and the operation at high temperature, low pressure and high N₂/MG ratio to enhance the yield of targeted GL. The insights demonstrated here from thermodynamics are valuable for guiding the design of catalysts and/or optimization of reaction conditions for the gas-phase synthesis of GL from MG.

Key words: Gas-phase synthesis, Glycolide, Methyl glycolate, Thermodynamics, Chemical reaction, Simulation

摘要： Gas-phase synthesis of glycolide (GL) from methyl glycolate (MG) is of great significance for producing biodegradable polyglycolic acid. Here, we report a detailed thermodynamics study for the gas-phase synthesis of GL from MG, which involves complex reaction pathways, by utilizing the Gibbs free energy minimization method. The results indicate that the decompositions of MG and GL and the polymerization of MG are thermodynamically favorable as compared with the target pathway, i.e., the cyclization of MG. Effects of the reaction conditions including temperature, pressure and feed composition on the formation of GL and linear polymers have also been addressed, which demonstrate that the higher temperature and lower pressure can effectively inhibit the formation of linear methyl ester dimer and improve the selectivity to GL. In addition, the higher N₂/MG ratio is beneficial for the formation of GL in the process promoted by catalysts. These thermodynamics results indicate that the process promoted by catalysts would benefit from the kinetics control by high-performance catalysts and the operation at high temperature, low pressure and high N₂/MG ratio to enhance the yield of targeted GL. The insights demonstrated here from thermodynamics are valuable for guiding the design of catalysts and/or optimization of reaction conditions for the gas-phase synthesis of GL from MG.

关键词: Gas-phase synthesis, Glycolide, Methyl glycolate, Thermodynamics, Chemical reaction, Simulation

Dai Zhang, Xiaofeng Xu, Yueqiang Cao, Wei Li, Jinghong Zhou, Xinggui Zhou. Thermodynamics insights into the gas-phase synthesis of glycolide from methyl glycolate[J]. Chinese Journal of Chemical Engineering, 2025, 81(5): 171-181.

Dai Zhang, Xiaofeng Xu, Yueqiang Cao, Wei Li, Jinghong Zhou, Xinggui Zhou. Thermodynamics insights into the gas-phase synthesis of glycolide from methyl glycolate[J]. 中国化学工程学报, 2025, 81(5): 171-181.

References

[1] K. Budak, O. Sogut, U. Aydemir Sezer, A review on synthesis and biomedical applications of polyglycolic acid, J. Polym. Res. 27 (8) (2020) 208.
[2] Z.Y. Zhang, Q. Peng, X.F. Shi, H. Niu, P. Guo, Z.W. Li, M.F. Lyu, M. Lei, A theoretical and experimental study on the degradation mechanism of polyglycolic acid under acidic, neutral, and basic conditions, J. Appl. Polym. Sci. 141 (37) (2024) e55947.
[3] Y. Reyhanoglu, B. Kalayci, E. Gokturk, One-step solvent-free synthesis of polyglycolic acid from sustainable C1 feedstocks, Macromol. Chem. Phys. 222 (2) (2021) 2000284.
[4] N.M. El-Sayed, M.A. El-Bakary, M.A. Ibrahim, M.A. Elgamal, A.A. Hamza, Characterization of the mechanical and structural properties of PGA/TMC copolymer for cardiac tissue engineering, Microsc. Res. Tech. 84 (7) (2021) 1596-1606.
[5] Y.Y. Lu, C. Schmidt, S. Beuermann, Fast synthesis of high-molecular-weight polyglycolide using diphenyl bismuth bromide as catalyst, Macromol. Chem. Phys. 216 (4) (2015) 395-399.
[6] Z. Pan, J.D. Ding, Poly(lactide-co-glycolide) porous scaffolds for tissue engineering and regenerative medicine, Interface Focus 2 (3) (2012) 366-377.
[7] G. Wang, S.J. Liu, S.W. Ueng, E.C. Chan, The release of cefazolin and gentamicin from biodegradable PLA/PGA beads, Int. J. Pharm. 273 (1-2) (2004) 203-212.
[8] K. Yamane, H. Sato, Y. Ichikawa, K. Sunagawa, Y. Shigaki, Development of an industrial production technology for high-molecular-weight polyglycolic acid, Polym. J. 46 (11) (2014) 769-775.
[9] V. Botvin, S. Karaseva, D. Salikova, M. Dusselier, Syntheses and chemical transformations of glycolide and lactide as monomers for biodegradable polymers, Polym. Degrad. Stab. 183 (2021) 109427.
[10] Y. Reyhanoglu, E. Gokturk, Synthesis of polyglycolic acid copolymers from cationic copolymerization of C1 feedstocks and long chain epoxides, J. Saudi Chem. Soc. 23 (7) (2019) 879-886.
[11] Y. Reyhanoglu, E. Sahmetlioglu, E. Gokturk, Alternative approach for synthesizing polyglycolic acid copolymers from C1 feedstocks and fatty ester epoxides, ACS Sustainable Chem. Eng. 7 (5) (2019) 5103-5110.
[12] D. Rik De Clercq, D. Ekaterina Makshina, P. .B.F. Sels, P. . Michiel Dusselier, Catalytic gas-phase cyclization of glycolate esters: a novel route toward glycolide-based bioplastics, ChemCatChem 10 (24) (2018) 5649-5655.
[13] M. Dusselier, P. Van Wouwe, A. Dewaele, P.A. Jacobs, B.F. Sels, GREEN CHEMISTRY. Shape-selective zeolite catalysis for bioplastics production, Science 349 (6243) (2015) 78-80.
[14] V. Botvin, A. Latypov, N. Ponarin, A. Filimoshkin, Synthesis of glycolide by catalytic depolymerization of glycolic acid oligomers modified by polyhydric alcohols, J. Phys.: Conf. Ser. 1145 (2019) 012019.
[15] R. De Clercq, M. Dusselier, E. Makshina, B.F. Sels, Catalytic gas-phase production of lactide from renewable alkyl lactates, Angew. Chem. Int. Ed 57 (12) (2018) 3074-3078.
[16] R. De Clercq, M. Dusselier, C. Poleunis, D.P. Debecker, L. Giebeler, S. Oswald, E. Makshina, B.F. Sels, Titania-silica catalysts for lactide production from renewable alkyl lactates: structure-activity relations, ACS Catal. 8 (9) (2018) 8130-8139.
[17] H.W. Park, Y.K. Chang, Economically efficient synthesis of lactide using a solid catalyst, Org. Process Res. Dev. 21 (12) (2017) 1980-1984.
[18] A. Vita, C. Italiano, D. Previtali, C. Fabiano, A. Palella, F. Freni, G. Bozzano, L. Pino, F. Manenti, Methanol synthesis from biogas: a thermodynamic analysis, Renew. Energy 118 (2018) 673-684.
[19] S.S. Iyer, T. Renganathan, S. Pushpavanam, M. Vasudeva Kumar, N. Kaisare, Generalized thermodynamic analysis of methanol synthesis: Effect of feed composition, J. CO₂ Util. 10 (2015) 95-104.
[20] B.Z. Yao, W.J. Ma, S. Gonzalez-Cortes, T.C. Xiao, P.P. Edwards, Thermodynamic study of hydrocarbon synthesis from carbon dioxide and hydrogen, Greenh. Gases Sci. Technol. 7 (5) (2017) 942-957.
[21] G. Pomalaza, R. De Clercq, M. Dusselier, B. Sels, How substituent effects influence the thermodynamics and kinetics of gas-phase transesterification of alkyl lactates to lactide using TiO₂/SiO₂, Appl. Catal. B Environ. 300 (2022) 120747.
[22] N.G. Zanjani, A.K. Pirzaman, E. Yazdanian, Biodiesel production in the presence of heterogeneous catalyst of alumina: Study of kinetics and thermodynamics, Int. J. Chem. Kinet. 52 (7) (2020) 472-484.
[23] S.J. Guo, H. Wang, Z.F. Qin, Z.K. Li, G.F. Wang, M. Dong, W.B. Fan, J.G. Wang, Feasibility, limit, and suitable reaction conditions for the production of alcohols and hydrocarbons from CO and CO₂ through hydrogenation, a thermodynamic consideration, Ind. Eng. Chem. Res. 61 (46) (2022) 17027-17038.
[24] M.S. Elmelawy, A. El-Meligy, H.A. Mawgoud, A.S. Morshedy, S.A. Hanafy, I.E. El-sayed, Synthesis and kinetics study of trimethylolpropane fatty acid triester from oleic acid methyl ester as potential biolubricant, Biomass Convers. Biorefin. 13 (3) (2023) 1645-1657.
[25] Y.N. Guan, H.Q. Ma, W.Y. Chen, M.S. Li, G. Qian, D. Chen, X.G. Zhou, X.Z. Duan, Methyl methacrylate synthesis: thermodynamic analysis for oxidative esterification of methacrolein and aldol condensation of methyl acetate, Ind. Eng. Chem. Res. 59 (39) (2020) 17408-17416.
[26] S.K. Kabra, E. Turpeinen, R.L. Keiski, G.D. Yadav, Direct synthesis of dimethyl carbonate from methanol and carbon dioxide: a thermodynamic and experimental study, J. Supercrit. Fluids 117 (2016) 98-107.
[27] M.M. Chen, K.L. Yan, Y.Q. Cao, Y.R. Li, X.H. Ge, J. Zhang, X.Q. Gong, G. Qian, X.G. Zhou, X.Z. Duan, Thermodynamics insights into the selective hydrogenation of alkynes in C₂ and C₃ streams, Ind. Eng. Chem. Res. 60 (47) (2021) 16969-16980.
[28] I. Banu, A.V. Brosteanu, G. Bumbac, G. Bozga, Ethanol conversion to butadiene: a thermodynamic analysis, Ind. Eng. Chem. Res. 60 (35) (2021) 13071-13083.
[29] Q.Y. Huang, Y. Li, F.H. Yuan, L.P. Xiao, H.X. Hao, Y.L. Wang, Thermodynamic properties of enantiotropic polymorphs of glycolide, J. Chem. Thermodyn. 111 (2017) 106-114.
[30] P. Koukkari, R. Pajarre, A Gibbs energy minimization method for constrained and partial equilibria, Pure Appl. Chem. 83 (6) 1243–1254.
[31] S.W. Benson, J.H. Buss, Additivity rules for the estimation of molecular properties. thermodynamic properties, 29 (3) (1958) 546-572.
[32] K. Shukla, V.C. Srivastava, Synthesis of diethyl carbonate from ethanol through different routes: a thermodynamic and comparative analysis, Can. J. Chem. Eng. 96 (1) (2018) 414-420.
[33] W. Prachumsai, S. Pangtaisong, S. Assabumrungrat, P. Bunruam, C. Nakvachiratrakul, D. Saebea, P. Praserthdam, S. Soisuwan, Carbon dioxide reduction to synthetic fuel on zirconia supported copper-based catalysts and Gibbs free energy minimization: Methanol and dimethyl ether synthesis, J. Environ. Chem. Eng. 9 (1) (2021) 104979.
[34] C. Tuygun, B. Ipek, CO₂ hydrogenation to methanol and dimethyl ether at atmospheric pressure using Cu-Ho-Ga/γ-Al₂O₃ and Cu-Ho-Ga/ZSM-5: Experimental study and thermodynamic analysis, Turk. J. Chem. 45 (1) (2021) 231-247.
[35] K. Stangeland, H.L. Li, Z.X. Yu, Thermodynamic analysis of chemical and phase equilibria in CO₂ hydrogenation to methanol, dimethyl ether, and higher alcohols, Ind. Eng. Chem. Res. 57 (11) (2018) 4081-4094.
[36] S. Adhikari, S. Fernando, S.R. Gwaltney, S.D. Filip To, R. Mark Bricka, P.H. Steele, A. Haryanto, A thermodynamic analysis of hydrogen production by steam reforming of glycerol, Int. J. Hydrog. Energy 32 (14) (2007) 2875-2880.
[37] C.V. Miguel, M.A. Soria, A. Mendes, L.M. Madeira, Direct CO₂ hydrogenation to methane or methanol from post-combustion exhaust streams-A thermodynamic study, J. Nat. Gas Sci. Eng. 22 (2015) 1-8.
[38] J. Liu, Z.Q. Li, M.W. Wang, X.X. Wan, S.Z. Jia, Y.C. Cao, Z.G. Gao, Solid-liquid phase equilibrium of N, N'-diphenyl thiourea (DPTU) in twelve pure solvents: Solubility determination, correlation, molecular simulation and thermodynamic analysis, J. Chem. Thermodyn. 163 (2021) 106605.
[39] M. Wang, H. Kaur, C.C. Chen, Thermodynamic modeling of HNO₃-H₂SO₄-H₂O ternary system with symmetric electrolyte NRTL model, AIChE. J. 63 (7) (2017) 3110-3117.

Thermodynamics insights into the gas-phase synthesis of glycolide from methyl glycolate

Thermodynamics insights into the gas-phase synthesis of glycolide from methyl glycolate

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Qinwen Liu, Guoqing Lian, Wenli Dong, Yu Su, Wei Quan Leong, Chi-Hwa Wang, Wenqi Zhong. A three-dimensional CFD numerical simulation study on pressurized oxy-fuel gasification of poultry manure in an industrial-scale gasifier [J]. Chinese Journal of Chemical Engineering, 2025, 81(5): 115-127.
[2]	Meixian Liu, Shuyun Xue, Yajun Zhang, Linjuan Pei, Zhanfeng Zheng. Screening suitable metal ion bridges for the construction of unimpeded dual carrier-transfer channels in carbon nitride photocatalyst [J]. Chinese Journal of Chemical Engineering, 2025, 80(4): 70-78.
[3]	Haoran Yin, Lili Mu, Yifeng Chen, Licheng Li, Kang Sun, Xiaoyan Ji. Improving CO₂ solubility in a hybrid sorbent of 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide/mesoporous titanium dioxide/water with confinement effect [J]. Chinese Journal of Chemical Engineering, 2025, 80(4): 100-109.
[4]	Xin Zhou, Ce Liu, Zhibo Zhang, Xinrui Song, Haiyan Luo, Weitao Zhang, Lianying Wu, Hui Zhao, Yibin Liu, Xiaobo Chen, Hao Yan, Chaohe Yang. Hybrid modelling incorporating reaction and mechanistic data for accelerating the development of isooctanol oxidation [J]. Chinese Journal of Chemical Engineering, 2025, 80(4): 166-183.
[5]	Li Wang, Shibo Wang, Huiqiang Yang, Yuling Zhai, Jianxin Xu. Research on fluid motion characteristics and structural evolution in reciprocating mixing tanks [J]. Chinese Journal of Chemical Engineering, 2025, 79(3): 120-134.
[6]	Lingbing Bu, Li Guo, Yingqi Luo, Wenhua Yin, Yi Wu, Hongyu Zhang. Oxygen distribution in bed and safety analysis during hydrogen purification process from oxygen-containing feed gas [J]. Chinese Journal of Chemical Engineering, 2025, 78(2): 24-32.
[7]	Mingqi Jiang, Zhuo Wang, Zhijian Sun, Jian Wang. A parallel chemical reaction optimization method based on preference-based multi-objective expected improvement [J]. Chinese Journal of Chemical Engineering, 2025, 78(2): 82-92.
[8]	Lejun Wu, Jingbo Gao, Jing Li, Haibo Liu, Qiang Sun. The investigation of Gemini surfactant effects on CH₄ and CO₂ hydrates [J]. Chinese Journal of Chemical Engineering, 2025, 77(1): 167-174.
[9]	Yun Zhou, Wenzhi Xia, Guangsheng Wei, Haichuan Wang. Impact of CO₂ as an oxidant on the decarburization and chromium retention and an approach for CO₂ recycling [J]. Chinese Journal of Chemical Engineering, 2025, 77(1): 203-206.
[10]	Limin Wang, Jinrong Duan, Bei Liu, Zhi Li, Guangjin Chen. The effect of ethylene-vinyl acetate copolymer on the formation process of wax crystals and hydrates [J]. Chinese Journal of Chemical Engineering, 2024, 73(9): 109-119.
[11]	Jie Zhang, Lei Shi, Chuanxian Li, Fei Yang, Bo Yao, Guangyu Sun. Research methods and devices for hydrate characteristics during oil and gas transportation: A review [J]. Chinese Journal of Chemical Engineering, 2024, 73(9): 130-145.
[12]	Jing Chen, Wenqi Zhong, Guanwen Zhou, Jinming Li, Shasha Ding. Desulfurization characteristics of slaked lime and regulation optimization of circulating fluidized bed flue gas desulfurization process—A combined experimental and numerical simulation study [J]. Chinese Journal of Chemical Engineering, 2024, 73(9): 163-175.
[13]	Kai Ji, Zhencheng Ye, Feng Qian. Reaction network design and hybrid modeling of S Zorb [J]. Chinese Journal of Chemical Engineering, 2024, 73(9): 301-310.
[14]	Baowei Niu, Yanjie Yi, Yuwen Wei, Fuzhen Zhang, Lili Wang, Li Xia, Xiaoyan Sun, Shuguang Xiang. Phase equilibrium data prediction and process optimizationin butadiene extraction process [J]. Chinese Journal of Chemical Engineering, 2024, 71(7): 1-12.
[15]	Junjie Cai, Xijian Li, Hao Sui, Honggao Xie. Study on the evolution of solid–liquid–gas in multi-scale pore methane in tectonic coal [J]. Chinese Journal of Chemical Engineering, 2024, 71(7): 122-131.