Transactions of Tianjin University

, Volume 24, Issue 2, pp 144–151 | Cite as

Kinetics Modeling of Calcium Formate Synthesis by Calcium Hydroxide Carbonylation

  • Zhenhua Li
  • Chunfang Xie
  • Weihan Wang
  • Jing Lv
  • Xinbin Ma
Research Article

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 

List of Symbols

a

Gas–liquid interfacial area (cm2/cm3)

Ci

Molar concentration of component i in the liquid film (mol/m3)

Ci*

Molar concentration of component i in the gas–liquid interface (mol/m3)

CiL

Molar concentration of component i in the liquid phase (mol/m3)

Di

Diffusion coefficient of component i in the liquid phase (cm2/s)

d

Impeller diameter (cm)

Ea

Activation energy of Eq. (21) (J/mol)

Fi

Flow rate of component i (mL/min)

g

Gravitational acceleration (m/s2)

Hi

Henry’s constant (Pa·m3/mol)

k

Carbonylation reaction rate constant (s−1)

k0

Pre-exponential constant of Eq. (21) (s−1)

kL

D A /δL, mass transfer coefficient in the liquid film (cm/s)

M

Hatta number, dimensionless

Mi

Molar weight of component i (g/mol)

mi

Mass of component i used in the reaction (g)

n

Stirring speed (s−1)

Pi

Partial pressure of component i in the gas phase (Pa)

Re

ρnd2/μ, Reynolds number, dimensionless

Ri

Reaction rate of component i (mol/(m3·s))

R

Gas constant (J/(mol·K))

Sc

μ/ρDA, Schmidt number, dimensionless

Sh

kLd/DA, Sherwood number, dimensionless

T

Temperature (K)

t

Time (min)

VL

Volume of liquid phase (m3)

vs

Superficial gas velocity (cm/s)

Z

Coordinate

Y

Yield of calcium formate (%)

Greek Symbols

α

1/L, liquid volume/liquid film volume, dimensionless

β

Enhancement factor, dimensionless

δL

Thickness of the liquid film (cm)

ζ

Z/δL, dimensionless

ηi

C i /C i * , dimensionless

μ

Liquid viscosity (g/(cm·s))  

ρ

Density (g/cm3)

σ

Surface tension (g/s)

ωi

Purity of component i (%)

Subscripts

XA

Carbon monoxide

XB

Calcium hydroxide

Notes

Acknowledgements

This study was supported by the National High-Tech Research and Development Program of China (“863” Program, No. 2012AA06A113).

Supplementary material

12209_2018_121_MOESM1_ESM.docx (123 kb)
Supplementary material 1 (DOCX 122 kb)

References

  1. 1.
    Blinova YV, Sudareva SV, Krinitsina TP et al (2005) Mechanism of the formation of silver-sheathed HTSC ceramics and its fine structure. Phys Met Metallogr 99(6):623–632Google Scholar
  2. 2.
    Antipov EV, Aleshin VA (2002) Physicochemical aspects of the synthesis of mercury-copper mixed oxide superconductors. Russ J Inorg Chem 47(4):464–472Google Scholar
  3. 3.
    Chernoplekov NA (2001) Superconductor technologies: state of the art and prospects of practical application. Vestn Ross Akad Nauk 71(4):303–319Google Scholar
  4. 4.
    Zhong GQ (2002) Synthesis and application of calcium formate used as feed additive. Sci Tec Cereals Oils Foods 10(1):23–24 (in Chinese) Google Scholar
  5. 5.
    Huang JH, Yang FM (2005) Synthesization and determination of calcium formate and its application in piglet feed. China Feed 16:16–17 (in Chinese) Google Scholar
  6. 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]Google Scholar
  7. 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)Google Scholar
  8. 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)Google Scholar
  9. 9.
    Procek E, Stolka A (1978) Sodium formate: PL, 9,985,1B1 [P]Google Scholar
  10. 10.
    Melnikov KA, Rogoznyj VV, Karmazina TP et al (1981) Method of preparing sodium formate: SU, 81,066,3A1 [P]Google Scholar
  11. 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)Google Scholar
  12. 12.
    Iwata M (1968) Reaction rate of formation of sodium formate under low pressure (2‒7 kg/cm2). Res Rep Nagaoka Tech Coll 4(4):307–313Google Scholar
  13. 13.
    Pohorecki R, Moniuk W, Kumur A et al (1987) Kinetics of sodium formate synthesis. Sci Bull-Lodz Tech Univ, Chem and Process Eng 8:391–406Google Scholar
  14. 14.
    Sirotkin GD (1953) Utilization of carbon monoxide in the production of sodium formate. J Appl Chem (Leningrad) 26:340–343Google Scholar
  15. 15.
    El-Zanfally S, Khalifa M, Abou-Zeid YM (1965) Derivatives of glutarimide likely to possess therapeutic activity. J Pharm Sci 54(3):467–469CrossRefGoogle Scholar
  16. 16.
    Ramachandran PA, Sharma MM (1969) Absorption with fast reaction in a slurry containing sparingly soluble fine particles. Chem Eng Sci 24(11):1681–1686CrossRefGoogle Scholar
  17. 17.
    Patwardhan AV, Sharma MM (1989) Kinetics of absorption of carbon monoxide in aqueous solutions of sodium hydroxide and aqueous calcium hydroxide slurries. Ind Eng Chem Res 28(1):5–9CrossRefGoogle Scholar
  18. 18.
    Chen JW, Xu GH, Li ZH et al (1993) Kinetics of regeneration reaction for CO coupling. J Chem Ind Eng 44(1):66–72 (in Chinese) Google Scholar
  19. 19.
    Poling BE, Prausnitz JM, John PO et al (2001) The properties of gases and liquids. McGraw-Hill, New YorkGoogle Scholar
  20. 20.
    Wilke CR, Chang P (1955) Correlation of diffusion coefficients in dilute solutions. AIChE J 1(2):264–270CrossRefGoogle Scholar
  21. 21.
    Versteeg GF, Blauwhoff PMM, Van Swaaij WPM (1987) The effect of diffusivity on gas-liquid mass transfer in stirred vessels. Experiments at atmospheric and elevated pressures. Chem Eng Sci 42(5):1103–1119CrossRefGoogle Scholar
  22. 22.
    Gilliland ER, Sherwood TK (1934) Diffusion of vapors into air streams. Ind Eng Chem 26(5):516–523CrossRefGoogle Scholar
  23. 23.
    Yagi H, Yoshida F (1975) Gas absorption by Newtonian and non-Newtonian fluids in sparged agitated vessels. Ind Eng Chem Process Des Dev 14(4):488–493CrossRefGoogle Scholar
  24. 24.
    Sideman S, Hortaçsu Ö, Fulton JW (2002) Mass transfer in gas-liquid contacting systems. Ind Eng Chem 58(7):32–47CrossRefGoogle Scholar

Copyright information

© Tianjin University and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Zhenhua Li
    • 1
    • 2
  • Chunfang Xie
    • 1
  • Weihan Wang
    • 1
  • Jing Lv
    • 1
  • Xinbin Ma
    • 1
    • 2
  1. 1.Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and TechnologyTianjin UniversityTianjinChina
  2. 2.Collaborative Innovation Center of Chemical Science and Engineering (Tianjin)Tianjin UniversityTianjinChina

Personalised recommendations