Skip to main content
Log in

Kinetics development for controlled mono-methyl amine-ethoxylation reaction using laboratory scale autoclave experiments and process plant reactor data simulations

  • Original Paper
  • Published:
Chemical Papers Aims and scope Submit manuscript

Abstract

A methodology using laboratory-scale autoclave reactor data and industrial process plant data is proposed to develop and validate the kinetics of controlled ethoxylation of mono-methyl amine (MMA) solution. Initially, the ethoxylation of mono-methyl amine solution was carried out using an autoclave reactor under isothermal conditions, and the rate of products: mono-methyl ethanolamine (MMEA), methyl-di-ethanol amine (MDEA), and glycol ethers of methyl-di-ethanol amine (MDEA-P) was established. Then, the Aspen Plus process simulator sensitivity analysis was performed with the variations in the kinetics model parameters to mimic the real plant product distribution. Finally, the amine-ethoxylation reaction kinetics was validated by comparing the activation energies obtained from classical kinetics modelling through autoclave reactor experiments and simulation-based real plant sensitivity analysis. From the results, Ea = 19.46 kcal/mol and A = 6.02*108 for MMEA formation, Ea = 4.2 kcal/mol and A = 21.12 for MDEA formation and Ea = 9.46 kcal/mol and A = 307 for MDEA-P formation, were found to be the optimized kinetic parameters from autoclave laboratory experiments and industrial reactor data simulations.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

References

  • ASTM D 2074 (1998) Standard test methods for total, primary, secondary, and tertiary amine values of fatty amines by alternative indicator method: D 2074. ASTM International, PA, US

  • Badgwell TA et al (1996) Aspen simulation of triethanol amine production process. EExxonMobil Corporation, Irving

    Google Scholar 

  • Dow Ltd. (2016a) Dow amines technical data sheet, Alkyl Alkanol Amine, Dow, 2001 (online). Available: www.dowamines.com. Accessed Dec 2016a

  • Dow Ltd (2016b) Dow Answer Center, Dow Chemical Company, 01 May 2016b (online). Available: https://dowac.custhelp.com/app/answers/detail/a_id/4412/kw/amine%20n...1%20of. Accessed 15 Dec 2016b.

  • Espinosa S, Diaz S, Brignole EA (2002) Thermodynamic modeling and process optimization of supercritical fluid fractionation of fish oil fatty acid ethyl esters. Ind Eng Chem Res 41:1516–1527

    Article  CAS  Google Scholar 

  • Eugeniusz M, Jan P, Halina P (1997) By-products of ethoxylation of diethylethanolamine and its solutions in methanol. Org Process Res Dev 1:379–383

    Article  Google Scholar 

  • Hammer H (1987) Ullman’s encyclopedia of industrial chemistry. Cambridge, New York

    Google Scholar 

  • Hatta M, Ito T, Miki M, Okabe T (1966) Reaction of ethylene oxide with ammonia. Yukagaku 5:215–220

    Google Scholar 

  • Hodgson AWE, Jacquinot P, Hauser PC (2000) Amperometric sensing of ethylene oxide in the gas phase. Anal Chem 72(10):2206–2210

    Article  CAS  PubMed  Google Scholar 

  • Kamal A-M (2017) Aspen plus: chemical engineering applications. Wiley, Hoboken

    Google Scholar 

  • Kataoka H (2005) Quantitaion of amino acids and amines by chromatography. J Chromatogr Lib 70:364–404

    Article  CAS  Google Scholar 

  • Kontogeorgis GM, Folas GK (2010) Thermodynamic models for industrial applications. Wiley, Hoboken

    Book  Google Scholar 

  • Kun L (2010) China Patent CN101781219 A

  • Laureano Jimenez JC-L (2002) The production of butyl acetate and methanol via reactive and extractive distillation. II. Process modeling, dynamic simulation, and control strategy. Ind Eng Chem Res 41:6735–6744

    Article  Google Scholar 

  • Levenspiel O (1961) Chemical reaction engineering, 3ed. Wiley, New York

    Google Scholar 

  • Luyben WL (2011) Principles and case studies of simultaneous design. Wiley, Hoboken

    Book  Google Scholar 

  • Mathias CCCPM (2002) Applied thermodynamics for process modeling. AIChE J 48(2):194–200

    Article  Google Scholar 

  • Namiesnik J, Jastrzebska A, Zygmunt B (2003) Determination of volatile aliphatic amines in air by solid-phase microextraction coupled with gas chromatography with flame ionization detection. J Chromatogr A 1016:1–9

    Article  CAS  PubMed  Google Scholar 

  • Pellegrini LA, Moioli S, Picutti B, Vergani P, Gamba S (2001) Design of an acidic natural gas purification plant by means of a process simulator. Oil Gas J Italy 7:192–205

    Google Scholar 

  • Robbins GD, Bullin JA (1984) Analysis of amine solutions by gas chromatography. Energy Progress December. Bryan Research and Engineering Inc, Texas, pp 229–232

    Google Scholar 

  • Ruehl C, Hou C, Lee P, Armstrong L (1997) Design of a system of ethanolamine reactors, Course project CENG 403. Rice University, Houston, Texas

    Google Scholar 

  • Sandler SI (2006) Chemical, biochemical, and engineering thermodynamics, 4th edn. Wiley, Hoboken

    Google Scholar 

  • Santacesaria E, Serio M, Lisi L, Geosa D (1990) Kinetics of nonylphenol polyethoxylation catalyzed by potassium hydroxide. Ind Eng Chem Res 29:719–725

    Article  CAS  Google Scholar 

  • Siggia S, Hanna JG, Kervenski IR (1950) Quantitative analysis of mixtures of primary, secondary, and tertiary aromatic amines. Anal Chem 22(10)

  • Sirovski F, Sergei Mulyashov VS (2005) Large-scale fatty amine ethoxylation reactor: a dynamic model. Chem Eng J 117:197–203

    Article  Google Scholar 

  • Stropoli SJ, Elrod MJ (2015) Assessing the potential for the reactions of epoxides with amines on secondary organic aerosol particles. J Phys Chem 115(119):10181–10189

    Article  Google Scholar 

  • Sundaram PK, Sharma MM (1968) Kinetics of reactions of amines with alkene oxides. Bull Chem Soc Jpn 42:3141–3147

    Article  Google Scholar 

  • Trejbal J, Petrisko M (2004) Kinetics of ethylenediamine and piperazine ethoxylation. React Kinet Catal Lett 82(2):339–346

    Article  CAS  Google Scholar 

  • Voutsas E, Vrachnos A, Magoulas K (2014) Measurement and thermodynamic modeling of the phase equilibrium of aqueous N-methyldiethanolamine solutions. Fluid Phase Equilib 224:193–197

    Article  Google Scholar 

  • Xavier A, Srividhya N (2014) Synthesis and study of Schiff base ligands. IOSR J Appl Chem 7(11):6–15

    Article  Google Scholar 

  • Yang C, Yang Feng BC, Zhang P, Qin Z, Zeng H, Sun F (2013) Vapor−liquid equilibria for three binary systems of N-methylethanolamine, N-methyldiethanolamine, and ethylene glycol at P = (40.0, 30.0, and 20.0) kPa. J Chem Eng Data 58:2272–2279

    Article  CAS  Google Scholar 

  • Zahedi G, Amraei S, Biglari M (2009) Simulation and optimization of ethanol amine production plant. Can J Chem Eng 26(6):1504–1511

    CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Raghu Raja Pandiyan Kuppusamy.

Ethics declarations

Conflict of interest

On behalf of all authors, the corresponding author states that there is no conflict of interest.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (XLSX 107 kb)

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Kuppusamy, R.R.P., Zade, A. & Neogi, S. Kinetics development for controlled mono-methyl amine-ethoxylation reaction using laboratory scale autoclave experiments and process plant reactor data simulations. Chem. Pap. 77, 1887–1906 (2023). https://doi.org/10.1007/s11696-022-02583-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11696-022-02583-5

Keywords

Navigation