Kinetics Modeling of Calcium Formate Synthesis by Calcium Hydroxide Carbonylation

Abstract

The synthesis of calcium formate by Ca(OH)₂ carbonylation was studied in a semi-batch stirred tank. The reaction mechanism was analyzed theoretically and the rate of each step was compared. The influence of reaction conditions on the formation of calcium formate was investigated. The results indicate that the rate-controlling step is the reaction between dissolved CO and dissolved Ca(OH)₂, and the gaseous diffusion resistance can be eliminated when the stirring speed reached 1000 r/min. Furthermore, the reaction kinetics was studied at a stirring speed of 1000 r/min, temperature of 423–453 K, pressure of 2.0–3.5 MPa and different initial concentrations of Ca(OH)₂. An effective method was proposed to measure the reaction rate of CO. A mathematical model was developed using the dual-film theory, and the parameters were obtained using regression of experimental data. The reaction rates calculated using the kinetics model were compared with experimental data. The results show that the deviations are within ±10%, proving that the established model is valid and can provide a basis for industrial amplification.

Keywords

Calcium hydroxide / Carbonylation / Calcium formate / Kinetics

References

[1] Blinova YV, Sudareva SV, Krinitsina TP, et al. Mechanism of the formation of silver-sheathed HTSC ceramics and its fine structure. Phys Met Metallogr, 2005, 99(6): 623-632.

[2] Antipov EV, Aleshin VA. Physicochemical aspects of the synthesis of mercury-copper mixed oxide superconductors. Russ J Inorg Chem, 2002, 47(4): 464-472.

[3] Chernoplekov NA. Superconductor technologies: state of the art and prospects of practical application. Vestn Ross Akad Nauk, 2001, 71(4): 303-319.

[4] Zhong GQ. Synthesis and application of calcium formate used as feed additive. Sci Tec Cereals Oils Foods, 2002, 10(1): 23-24 (in Chinese)

[5] Huang JH, Yang FM. Synthesization and determination of calcium formate and its application in piglet feed. China Feed, 2005, 16: 16-17 (in Chinese)

[6] Awane Y, Nagata M, Otsuka S et al (1975) Process for the continuous production of highly pure sodium formate: US, 3,928,435 [P]

[7] Guo HC, Jiang HJ, Zheng RH (2016) Method for preparing sodium formate by using carbon monoxide under palladium catalysis: CN, 102,936,193 [P]. (in Chinese)

[8] Li A, Shen J, Kang YB (2007) Process for preparing sodium formate using carbon oxide in carbide furnace and coke furnace tail gas: CN, 1,010,702,80A [P]. (in Chinese)

[9] Procek E, Stolka A (1978) Sodium formate: PL, 9,985,1B1 [P]

[10] Melnikov KA, Rogoznyj VV, Karmazina TP et al (1981) Method of preparing sodium formate: SU, 81,066,3A1 [P]

[11] Zhang SH, Yuan JH (2007) Process for producing sodium formate from carbonic oxide in synthesis ammonia raw material gas: CN, 1,010,331,83A [P]. (in Chinese)

[12] Iwata M. Reaction rate of formation of sodium formate under low pressure (2‒7 kg/cm²). Res Rep Nagaoka Tech Coll, 1968, 4(4): 307-313.

[13] Pohorecki R, Moniuk W, Kumur A, et al. Kinetics of sodium formate synthesis. Sci Bull-Lodz Tech Univ, Chem and Process Eng, 1987, 8: 391-406.

[14] Sirotkin GD. Utilization of carbon monoxide in the production of sodium formate. J Appl Chem (Leningrad), 1953, 26: 340-343.

[15] El-Zanfally S, Khalifa M, Abou-Zeid YM. Derivatives of glutarimide likely to possess therapeutic activity. J Pharm Sci, 1965, 54(3): 467-469.

[16] Ramachandran PA, Sharma MM. Absorption with fast reaction in a slurry containing sparingly soluble fine particles. Chem Eng Sci, 1969, 24(11): 1681-1686.

[17] Patwardhan AV, Sharma MM. Kinetics of absorption of carbon monoxide in aqueous solutions of sodium hydroxide and aqueous calcium hydroxide slurries. Ind Eng Chem Res, 1989, 28(1): 5-9.

[18] Chen JW, Xu GH, Li ZH, et al. Kinetics of regeneration reaction for CO coupling. J Chem Ind Eng, 1993, 44(1): 66-72 (in Chinese)

[19] Poling BE, Prausnitz JM, John PO, et al. The properties of gases and liquids, 2001, New York: McGraw-Hill.

[20] Wilke CR, Chang P. Correlation of diffusion coefficients in dilute solutions. AIChE J, 1955, 1(2): 264-270.

[21] Versteeg GF, Blauwhoff PMM, Van Swaaij WPM. The effect of diffusivity on gas-liquid mass transfer in stirred vessels. Experiments at atmospheric and elevated pressures. Chem Eng Sci, 1987, 42(5): 1103-1119.

[22] Gilliland ER, Sherwood TK. Diffusion of vapors into air streams. Ind Eng Chem, 1934, 26(5): 516-523.

[23] Yagi H, Yoshida F. Gas absorption by Newtonian and non-Newtonian fluids in sparged agitated vessels. Ind Eng Chem Process Des Dev, 1975, 14(4): 488-493.

[24] Sideman S, Hortaçsu Ö, Fulton JW. Mass transfer in gas-liquid contacting systems. Ind Eng Chem, 2002, 58(7): 32-47.