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Reaction kinetics of the production of polyoxymethylene dimethyl ethers from methanol and formaldehyde with acid cation exchange resin catalyst

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Abstract

The synthesis of polyoxymethylene dimethyl ethers (PODEn) from methanol and formaldehyde was studied in a fixed bed reactor over the strong acid cation exchange resin catalyst. First, the influence of operating parameters such as temperature and WHSV on reactions was investigated. The conversion of methanol and formaldehyde was improved by increasing temperature. Second, a kinetic equation was derived to estimate the reaction rate constant of methanol and formaldehyde towards PODE. The reaction rate and kinetic model with six PODEn-synthesis reactions was established. We used a fourth order Runge–Kutta method and quasi-Newton method to solve the kinetic equations. The values of apparent activation energies of the six reactions are between 38.58 and 43.68 kJ mol−1. Ultimately, a mechanism was proposed to explain the results of apparent activation energy. The rate equations that were developed could predict the behavior of the synthesis of PODEn from methanol and formaldehyde reasonably well.

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Abbreviations

PODEn :

Polyoxymethylene dimethyl ethers

WHSV:

Weight hourly space velocity

HD-S:

Hydrogen form acid cation exchange resin

FID:

Flame ionization detector

TCD:

Thermal conductivity detector

GC:

Gas chromatograph

n i :

Amount of component i in the bulk

r PODEn :

Reaction rate of PODEn synthesis reaction

C i :

Concentration of component i in the bulk

k an :

Apparent rate constant of PODEn synthesis reaction

k n :

Rate constant of PODEn synthesis reaction

E n :

Apparent activation energy of PODEn synthesis reaction

T :

Reaction temperature

X i :

Molar content of component i in the bulk

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Authors and Affiliations

  1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai, 200237, China

    Jianqiang Zhang, Minhao Shi, Dingye Fang & Dianhua Liu

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  1. Jianqiang Zhang
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  2. Minhao Shi
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  3. Dingye Fang
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  4. Dianhua Liu
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Correspondence to Dianhua Liu.

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Zhang, J., Shi, M., Fang, D. et al. Reaction kinetics of the production of polyoxymethylene dimethyl ethers from methanol and formaldehyde with acid cation exchange resin catalyst. Reac Kinet Mech Cat 113, 459–470 (2014). https://doi.org/10.1007/s11144-014-0771-6

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  • DOI: https://doi.org/10.1007/s11144-014-0771-6

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