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

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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.

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  • 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: Accessed Dec 2016a

  • Dow Ltd (2016b) Dow Answer Center, Dow Chemical Company, 01 May 2016b (online). Available: 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 

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Correspondence to Raghu Raja Pandiyan Kuppusamy.

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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).

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