Experimental results for the vapor-liquid equilibria of (formaldehyde + 1,3,5-trioxane + methanol + salt + water) systems and comparison with predictions

doi:10.1016/j.cjche.2020.11.019

Chinese Journal of Chemical Engineering ›› 2021, Vol. 32 ›› Issue (4): 291-300.DOI: 10.1016/j.cjche.2020.11.019

• Chemical Engineering Thermodynamics • Previous Articles Next Articles

Experimental results for the vapor-liquid equilibria of (formaldehyde + 1,3,5-trioxane + methanol + salt + water) systems and comparison with predictions

Xianming Zhang^1,2, Mengchen Li³, Yufeng Hu¹, Zhichang Liu¹, Shuqin Mo¹

1 State Key Laboratory of Heavy Oil Processing and High Pressure Fluid Phase Behavior&Property Research Laboratory, China University of Petroleum, Beijing 102249, China;
2 School of Chemical Engineering, Ordos Institute of Technology, Ordos 017000, China;
3 PetroChina Petrochemical Research Institute Science Base PetroChina, Beijing 102206, China

Received:2020-09-09 Revised:2020-11-08 Online:2021-06-19 Published:2021-04-28
Contact: Yufeng Hu, Zhichang Liu
Supported by:
The authors gratefully acknowledge financial support from the National Natural Science Foundation of China (grant numbers 22078355, 21890763 and 21776300), Petrochemical Research Institute of PetroChina (grant number HX20200668), and Scientific Research Project of Ordos Institute of Technology (grant numbers KYYB2019006).

Experimental results for the vapor-liquid equilibria of (formaldehyde + 1,3,5-trioxane + methanol + salt + water) systems and comparison with predictions

Xianming Zhang^1,2, Mengchen Li³, Yufeng Hu¹, Zhichang Liu¹, Shuqin Mo¹

1 State Key Laboratory of Heavy Oil Processing and High Pressure Fluid Phase Behavior&Property Research Laboratory, China University of Petroleum, Beijing 102249, China;
2 School of Chemical Engineering, Ordos Institute of Technology, Ordos 017000, China;
3 PetroChina Petrochemical Research Institute Science Base PetroChina, Beijing 102206, China

通讯作者: Yufeng Hu, Zhichang Liu
基金资助:
The authors gratefully acknowledge financial support from the National Natural Science Foundation of China (grant numbers 22078355, 21890763 and 21776300), Petrochemical Research Institute of PetroChina (grant number HX20200668), and Scientific Research Project of Ordos Institute of Technology (grant numbers KYYB2019006).

Abstract

Abstract: The salt effect on the vapor-liquid phase equilibrium (VLE) of solvent mixtures is of significant interest in the industrial production of 1,3,5-trioxane. Experimental data for the VLE of quinary systems (formaldehyde + 1,3,5-trioxane + methanol + salt + water) and their ternary subsystems (formaldehyde + salt + water), (1,3,5-trioxane + salt + water), and (methanol + salt + water) were systematic measured under atmospheric pressure. The salts considered included KBr, NaNO₃, and CaCl₂. The extended UNIFAC model was used to describe the VLE of the salt-containing reactive mixtures. The model parameters were determined from the experimental VLE data of ternary systems or obtained from the literature, and then were used to predict the VLE of systems (1,3,5-trioxane + KBr + water), (methanol + KBr + water), (formaldehyde + KBr + water), and (formaldehyde + 1,3,5-trioxane + methanol + salt + water) with salt=KBr, NaNO₃, and CaCl₂. The predicted results showed good agreements with the measured results. Furthermore, the model was used to uncover the salt effect on the VLE of these multisolvent reactive systems.

Key words: Vapor liquid equilibria, Reactive distillation, Activity coefficient, 1,3,5-Trioxane production, UNIFAC, Salt effect

摘要： The salt effect on the vapor-liquid phase equilibrium (VLE) of solvent mixtures is of significant interest in the industrial production of 1,3,5-trioxane. Experimental data for the VLE of quinary systems (formaldehyde + 1,3,5-trioxane + methanol + salt + water) and their ternary subsystems (formaldehyde + salt + water), (1,3,5-trioxane + salt + water), and (methanol + salt + water) were systematic measured under atmospheric pressure. The salts considered included KBr, NaNO₃, and CaCl₂. The extended UNIFAC model was used to describe the VLE of the salt-containing reactive mixtures. The model parameters were determined from the experimental VLE data of ternary systems or obtained from the literature, and then were used to predict the VLE of systems (1,3,5-trioxane + KBr + water), (methanol + KBr + water), (formaldehyde + KBr + water), and (formaldehyde + 1,3,5-trioxane + methanol + salt + water) with salt=KBr, NaNO₃, and CaCl₂. The predicted results showed good agreements with the measured results. Furthermore, the model was used to uncover the salt effect on the VLE of these multisolvent reactive systems.

关键词: Vapor liquid equilibria, Reactive distillation, Activity coefficient, 1,3,5-Trioxane production, UNIFAC, Salt effect

Xianming Zhang, Mengchen Li, Yufeng Hu, Zhichang Liu, Shuqin Mo. Experimental results for the vapor-liquid equilibria of (formaldehyde + 1,3,5-trioxane + methanol + salt + water) systems and comparison with predictions[J]. Chinese Journal of Chemical Engineering, 2021, 32(4): 291-300.

References

[1] A. Curioni, M. Sprik, W. Andreoni, H. Schiffer, J. Hutter, M. Parrinello, Density functional theory-based molecular dynamics simulation of acid-catalyzed chemical reactions in liquid trioxane, J. Am. Chem. Soc. 119(31) (1997) 7218-7229.
[2] J. Masamoto, K. Hamanaka, K. Yoshida, H. Nagahara, K. Kagawa, T. Iwaisako, H. Komaki, Synthesis of trioxane using heteropolyacids as catalyst, Angew. Chem. Int. Ed. 39(12) (2000) 2102-2104.
[3] J. Qi, Y. Hu, H. Wang, W. Ma, S. Jiang, L. Yin, X. Zhang, Z. Yang, New reactions determine the yield and selectivity of 1,3,5-trioxane, Chem. Eng. J. 331(2018) 311-316.
[4] X. Zhang, Y. Hu, W. Ma, A model for the reaction kinetics of main and side reactions during the industrial production of trioxane, and its applications, J. Chem. Technol. Biotechnol. 93(2018) 2111-2117.
[5] X. Zhang, Y. Hu, W. Ma, J. Qi, S. Mo, Vapor-liquid and chemical equilibria model for formaldehyde +1,3,5-trioxane + methanol + salt + water system, Fluid Phase Equilib. 507(2020) 112434.
[6] T. Grützner, H. Hasse, N. Lang, M. Siegert, E. Ströfer, Development of a new industrial process for trioxane production, Chem. Eng. Sci. 62(2007) 5613-5620.
[7] Z. Bai, H. Liu, Y. Liu, Y. Fu, J. Zhao, X. Pu, Density, excess molar volume, and COSMO-RS study of reactive aqueous solutions containing formaldehyde, Fluid Phase Equilib. 474(2018) 83-91.
[8] H. Liu, Z. Bai, Y. Liu, X. Guo, Y. Fu, X. Pu, Interpretation and prediction of the vapor-liquid equilibrium of formaldehyde-water-methanol ternary system by the conductor-like screening model for real solvents, Fluid Phase Equilib. 429(2016) 233-241.
[9] C. Kuhnert, M. Albert, S. Breyer, I. Hahnenstein, H. Hasse, G. Maurer, Phase equilibrium in formaldehyde containing multicomponent mixtures:experimental results for fluid phase equilibria of (formaldehyde +(water or methanol) + methylal)) and (formaldehyde + water + methanol + methylal) and comparison with predictions, Ind. Eng. Chem. Res. 45(14) (2006) 5155-5164.
[10] G. Maurer, Vapor-liquid equilibrium of formaldehyde- and water-containing multicomponent mixtures, AIChE J. 32(6) (1986) 932-948.
[11] M. Hu, X.G. Zhou, W.K. Yuan, Simulation and optimization of a coupled reactor/column system for trioxane synthesis, Chem. Eng. Sci. 54(1999) 1353-1358.
[12] B. Sander, A. Fredenslund, P. Rasmussen, Calculation of vapour-liquid equilibria in mixed solvent/salt systems using an extended UNIQUAC equation, Chem. Eng. Sci. 41(1986) 1171-1183.
[13] K. Thomsen, M.C. Iliuta, P. Rasmussen, Extended UNIQUAC model for correlation and prediction of vapor-liquid-liquid-solid equilibria in aqueous salt systems containing non-electrolytes. Part B. Alcohol (ethanol, propanols, butanols)-water-salt systems, Chem. Eng. Sci. 59(2004) 3631-3647.
[14] G.B. Erdakos, W.E. Asher, J.H. Seinfeld, J.F. Pankow, Prediction of activity coefficients in liquid aerosol particles containing organic compounds, dissolved inorganic salts, and water-Part 1:Organic compounds and water by consideration of short- and long-range effects using X-UNIFAC.1, Atmos. Environ. 40(2006) 6410-6421.
[15] C. Shen, X. Li, Y. Lu, C. Li, Effect of ionic liquid 1-methylimidazolium chloride on the vapour liquid equilibrium of water, methanol, ethanol, and water + ethanol mixture, J. Chem. Thermodyn. 43(2011) 1748-1753.
[16] X. Li, C. Shen, C. Li, Effect of alkanolammonium formates ionic liquids on vapour liquid equilibria of binary systems containing water, methanol, and ethanol, J. Chem. Thermodyn. 53(2012) 167-175.
[17] Z. Lei, X. Xi, C. Dai, J. Zhu, B. Chen, Extractive distillation with the mixture of ionic liquid and solid inorganic salt as entrainers, AIChE J. 60(2014) 2994-3004.
[18] G. Yu, Y. Jiang, J. Cheng, Z. Lei, Structural effect on the vapor-liquid equilibrium of toluene-ionic liquid systems, Chem. Eng. Sci. 198(2019) 1-15.
[19] J.F. Morrison, J.C. Baker, H.C. Meredith, K.E. Newman, T.D. Walter, J.D. Massie, R.L. Perry, P.T. Cummings, Experimental measurement of vapor-liquid equilibrium in alcohol/water/salt systems, J. Chem. Eng. Data 35(4) (1990) 395-404.
[20] J. Dhanalakshmi, P.S.T. Sai, A.R. Balakrishnan, Effect of inorganic salts on the isobaric vapor-liquid equilibrium of the ethyl acetate-ethanol system, J. Chem. Eng. Data 58(3) (2013) 560-569.
[21] H. Hasse, I. Hahnenstein, G. Maurer, Revised vapor-liquid equilibrium model for multicomponent formaldehyde mixtures, AIChE J. 36(12) (1990) 1807-1814.
[22] M. Albert, B.C. García, C. Kreiter, G. Maurer, Vapor-liquid and chemical equilibria of formaldehyde-water mixtures, AIChE J. 45(9) (1999) 2024-2033.
[23] I. Kikic, M. Fermeglia, P. Rasmussen, UNIFAC prediction of vapor-liquid equilibria in mixed solvent-salt systems, Chem. Eng. Sci. 46(1991) 2775-2780.
[24] A. Fredenslund, R.L. Jones, J.M. Prausnitz, Group-contribution estimation of activity coefficients in nonideal liquid mixtures, AIChE J. 21(6) (1975) 1086-1099.
[25] A. Fredenslund, J. Gmehling, P. Rasmussen, Vapor-Liquid Equilibria Using UNIFAC:A Group-Contribution Method, Elsevier Scientific Publishing, New York, 1977.
[26] J. Li, Y. Lin, J. Gmehling, g E Model for single- and mixed-solvent electrolyte systems. 3. Prediction of salt solubilities in aqueous electrolyte systems, Ind. Eng. Chem. Res. 44(5) (2005) 1602-1609.
[27] M. Albert, H. Hasse, C. Kuhnert, G. Maurer, New experimental results for the vapor-liquid equilibrium of the binary system (trioxane + water) and the ternary system (formaldehyde + trioxane + water), J. Chem. Eng. Data 50(4) (2005) 1218-1223.
[28] A. Mohs, J. Gmehling, A revised LIQUAC and LIFAC model (LIQUAC*/LIFAC*) for the prediction of properties of electrolyte containing solutions, Fluid Phase Equilibr. 337(2013) 311-322.
[29] D.R. Lide, CRC Handbook of Chemistry and Physics, Internet Version 2005, CRC Press, Boca Raton, FL, 2005.
[30] E.C. Ihmels, J. Gmehling, Extension and Revision of the Group Contribution Method GCVOL for the Prediction of Pure Compound Liquid Densities, Ind. Eng. Chem. Res. 42(2) (2003) 408-412.
[31] O. Madelung, Static Dielectric Constants of Pure Liquids and Binary Liquid Mixtures, Springer-Verlag, Berlin, 1991.
[32] A.S. Lileev, P.S. Yastremskii, A.K. Lyashchenko, Structure and dielectric properties of aqueous solutions of formaldehyde and acetaldehyde, J. Struct. Chem. 21(1981) 517-521.
[33] P.S. Albright, L.J. Gosting, Dielectric constants of the methanol-water system from 5 to 55°, J. Am. Chem. Soc. 68(1946) 1061-1063.
[34] Y.i. Ming, L.M. Russell, Thermodynamic equilibrium of organic-electrolyte mixtures in aerosol particles, AIChE J. 48(6) (2002) 1331-1348.
[35] K.R. Patil, S.K. Chaudhari, S.S. Katti, Thermodynamic properties of aqueous electrolyte solutions. 3. Vapor pressure of aqueous solutions of LiNO₃, LiCl + LiNO₃, and LiBr + LiNO₃, J. Chem. Eng. Data 37(1) (1992) 136-138.
[36] W.D. Bancroft, H.L. Davis, The boiling-points of aqueous solutions, J. Phys. Chem. 33(1928) 591-604.
[37] X. Xu, Y. Hu, L. Wu, S. Zhang, Experimental and modeling of vapor-liquid equilibria for electrolyte solution systems, J. Chem. Eng. Data 59(2014) 3741-3748.

Experimental results for the vapor-liquid equilibria of (formaldehyde + 1,3,5-trioxane + methanol + salt + water) systems and comparison with predictions

Experimental results for the vapor-liquid equilibria of (formaldehyde + 1,3,5-trioxane + methanol + salt + water) systems and comparison with predictions

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Eileen Katherine Coronado-Aldana, Cindy Lizeth Ferreira-Salazar, Nubia Yineth Piñeros-Castro, Rubén Vázquez-Medina, Felipe A. Perdomo. Thermodynamic analysis, synthesis, characterization, and evaluation of 1-ethyl-3-methylimidazolium chloride: Study of its effect on pretreated rice husk [J]. Chinese Journal of Chemical Engineering, 2023, 60(8): 143-154.
[2]	Xiaomin Qiu, Yuanyuan Shen, Zhengkun Hou, Qi Wang, Zhaoyou Zhu, Yinglong Wang, Jingwei Yang, Jun Gao. Mechanism analysis of solvent selectivity and energy-saving optimization in vapor recompression-assisted extractive distillation for separation of binary azeotrope [J]. Chinese Journal of Chemical Engineering, 2022, 46(6): 271-279.
[3]	Nuochen Zhang, Yuande Dai, Linghao Feng, Biao Li. Study on environmentally friendly refrigerant R13I1/R152a as an alternative for R134a in automotive air conditioning system [J]. Chinese Journal of Chemical Engineering, 2022, 44(4): 292-299.
[4]	Ran An, Shengxin Chen, Shun Hou, Yuting Zhu, Chunhu Li, Xinbao Zhu, Ruixia Liu, Weizhong An. Simulation and design of a heat-integrated double-effect reactive distillation process for propylene glycol methyl ether production [J]. Chinese Journal of Chemical Engineering, 2022, 52(12): 103-114.
[5]	Zhiwei Wang, Jiannan Shi, Xiaonan Liu, Zhikai Cao, Yong Sha. Supported catalytic packing prepared from ceramic packing for reactive distillation of ethyl acetate [J]. Chinese Journal of Chemical Engineering, 2022, 50(10): 205-214.
[6]	Li Sun, Jierong Liang. Thermodynamic modeling of gas solubility in aqueous sodium chloride solution [J]. Chinese Journal of Chemical Engineering, 2021, 38(10): 184-195.
[7]	Songsong Chen, Li Dong, Junping Zhang, Weiguo Cheng, Feng Huo, Qian Su, Wei Hua. Effects of imidazolium-based ionic liquids on the isobaric vapor-liquid equilibria of methanol + dimethyl carbonate azeotropic systems [J]. Chinese Journal of Chemical Engineering, 2020, 28(3): 766-776.
[8]	Yu Ji, Tengda Zhang, Xia Gui, Haijian Shi, Zhi Yun. Solventless ketalization of glycerol to solketal with acetone over the ionic liquid[P(C₄H₉)₃C₁₄H₂₉][TsO] [J]. Chinese Journal of Chemical Engineering, 2020, 28(1): 158-164.
[9]	Chunli Li, Cong Duan, Jing Fang, Hongshi Li. Process intensification and energy saving of reactive distillation for production of ester compounds [J]. Chinese Journal of Chemical Engineering, 2019, 27(6): 1307-1323.
[10]	Lijing Zang, Kejin Huang, Ting Guo, Yang Yuan, Haisheng Chen, Liang Zhang, Xing Qian, Shaofeng Wang. Temperature inferential control of a reactive distillation column with double reactive sections [J]. Chinese Journal of Chemical Engineering, 2019, 27(4): 896-904.
[11]	Dewi Selvia Fardhyanti, Bayu Triwibowo, Heri Istanto, Muhammad Khusni Anajib, Amalia Larasati, Windy Oktaviani. Liquid phase equilibrium of phenol extraction from bio-oil produced by biomass pyrolysis using thermodynamic models [J]. Chin.J.Chem.Eng., 2019, 27(2): 391-399.
[12]	Xiaomei Ling, Yiwei Xie, Xiaocheng Lin, Ling Li, Ting Qiu. Porous polymer microsphere functionalized with benzimidazolium based ionic liquids as effective solid catalysts for esterification [J]. Chinese Journal of Chemical Engineering, 2019, 27(10): 2455-2466.
[13]	Yun Chen, Kangning Xiong, Shuai Shen, Huimin Wang, Shaoming Zhou, Libo Li. Salt effect on the liquid-liquid equilibrium of the ternary (water + phenol + methyl isobutyl ketone) system: Experimental data and correlation [J]. Chin.J.Chem.Eng., 2019, 27(1): 168-173.
[14]	Md. Anamul Hoque, Md. Masud Alam, Mohammad Robel Molla, Shahed Rana, Malik Abdul Rub, Mohammad A. Halim, Mohammed Abdullah Khan, Farida Akhtar. Interaction of cetyltrimethylammonium bromide with drug in aqueous/electrolyte solution: A combined conductometric and molecular dynamics method study [J]. Chin.J.Chem.Eng., 2018, 26(1): 159-167.
[15]	Zhixian Huang, Yixiong Lin, Xiaoda Wang, Changshen Ye, Ling Li. Optimization and control of a reactive distillation process for the synthesis of dimethyl carbonate [J]. , 2017, 25(8): 1079-1090.