Transactions of Tianjin University

, Volume 25, Issue 1, pp 1–8 | Cite as

A Synthesis, Process Optimization, and Mechanism Investigation for the Formation of Polyoxymethylene Dimethyl Ethers

  • Yang Liu
  • Yan Wang
  • Wangfeng CaiEmail author
Research Article


Polyoxymethylene dimethyl ethers (DMMn) are promising diesel additives. The synthesis of DMMn from methylal (DMM) and paraformaldehyde over the NKC-9 acidic ion-exchange resin catalyst was investigated. Many unrecyclable by-products such as methyl formate, dimethyl ether and formic acid were produced in the reaction. To increase the selectivity of the desired products DMM3‒6 and reduce the amount of unrecyclable by-products, the effects of reaction temperature, time, pressure and the molar ratio of the raw materials were evaluated through a series of single factor experiments. Experiments revealed that trace amount of water could suppress the formation of unrecyclable by-products, and the optimum initial water content (less than 2 wt%) was investigated. In addition, the synthetic process needs to go through the polyoxymethylene hemiformals intermediate stage, and then the DMMn were obtained when polyoxymethylene hemiformals reacted with methanol. Ultimately, a possible mechanism is proposed to describe the formation of DMMn from polyoxymethylene hemiformals in detail, in which it is revealed that the formation of carbocation intermediates is important in the reaction processes.


Polyoxymethylene dimethyl ethers Paraformaldehyde Methylal Diesel additive Polyoxymethylene hemiformals 


  1. 1.
    Zhao Q, Wang H, Qin ZF et al (2011) Synthesis of polyoxymethylene dimethyl ethers from methanol and trioxymethylene with molecular sieves as catalysts. J Fuel Chem Technol 39(12):918–923CrossRefGoogle Scholar
  2. 2.
    Burger J, Siegert M, Stroefer E et al (2010) Poly(oxymethylene) dimethyl ethers as components of tailored diesel fuel: Properties, synthesis and purification concepts. Fuel 89(11):3315–3319CrossRefGoogle Scholar
  3. 3.
    Burger J, Stroefer E, Hasse H (2012) Chemical equilibrium and reaction kinetics of the heterogeneously catalyzed formation of poly(oxymethylene) dimethyl ethers from methylal and trioxane. Ind Eng Chem Res 51(39):12751–12761CrossRefGoogle Scholar
  4. 4.
    Zhao YP, Xu Z, Chen H et al (2013) Mechanism of chain propagation for the synthesis of polyoxymethylene dimethyl ethers. J Energy Chem 22(6):833–836CrossRefGoogle Scholar
  5. 5.
    Yang CJ, Jackson RB (2012) China’s growing methanol economy and its implications for energy and the environment. Energy Policy 41:878–884CrossRefGoogle Scholar
  6. 6.
    Liu KJ, Zhang CF, Li RF (2013) Recent progress in polyoxymethylene dimethyl ether. Chem Ind Eng Prog 32(11):2593–2598Google Scholar
  7. 7.
    Zhang JQ, Fang DY, Liu DH (2014) Evaluation of Zr-Alumina in production of polyoxymethylene dimethyl ethers from methanol and formaldehyde: performance tests and kinetic investigations. Ind Eng Chem Res 53(35):13589–13597CrossRefGoogle Scholar
  8. 8.
    Zhang JQ, Shi MH, Fang DY et al (2014) Reaction kinetics of the production of polyoxymethylene dimethyl ethers from methanol and formaldehyde with acid cation exchange resin catalyst. React Kinet Mech and Catal 113(2):459–470MathSciNetCrossRefGoogle Scholar
  9. 9.
    Arvidson M, Fakley ME, Spencer MS (1987) Lithium halide-assisted formation of polyoxymethylene dimethyl ethers from dimethoxymethane and formaldehyde. J Mol Catal 41(3):391–393CrossRefGoogle Scholar
  10. 10.
    Moulton DS, Naegeli DW. Diesel fuel having improved qualities and method of forming: US, 5,746,785 [P]. 1998-5-5Google Scholar
  11. 11.
    Wu Q, Wang M, Hao Y et al (2014) Synthesis of polyoxymethylene dimethyl ethers catalyzed by Br Ønsted acid ionic liquids with alkanesulfonic acid groups. Ind Eng Chem Res 53(42):16254–16260CrossRefGoogle Scholar
  12. 12.
    Wu Q, Li WJ, Wang M et al (2015) Synthesis of polyoxymethylene dimethyl ethers from methylal and trioxane catalyzed by Br Ønsted acid ionic liquids with different alkyl groups. RSC Adv 5(71):57968–57974CrossRefGoogle Scholar
  13. 13.
    Zhang X, Wu P, Zhang Y et al (2014) Synthesis of polyoxymethylene dimethyl ethers with HMCM-22 zeolite loading phosphotungstic acid as catalyst. Chem React Eng Technol 30(2):140–144Google Scholar
  14. 14.
    Li HJ, Song HL, Chen LW et al (2015) Designed SO4 2−/Fe2O3-SiO2 solid acids for polyoxymethylene dimethyl ethers synthesis: the acid sites control and reaction pathways. Appl Catal B 165:466–476CrossRefGoogle Scholar
  15. 15.
    Harmer MA, Sun Q (2001) Solid acid catalysis using ion-exchange resins. Appl Catal A 221(1–2):45–62CrossRefGoogle Scholar
  16. 16.
    Shibasaki-Kitakawa N, Honda H, Kuribayashi H et al (2007) Biodiesel production using anionic ion-exchange resin as heterogeneous catalyst. Bioresour Technol 98(2):416–421CrossRefGoogle Scholar
  17. 17.
    Zheng YY, Tang Q, Wang TF et al (2013) Synthesis of a green diesel fuel additive over cation resins. Chem Eng Technol 36(11):1951–1956CrossRefGoogle Scholar
  18. 18.
    Zheng YY, Tang Q, Wang TF et al (2015) Kinetics of synthesis of polyoxymethylene dimethyl ethers from paraformaldehyde and dimethoxymethane catalyzed by ion-exchange resin. Chem Eng Sci 134:758–766CrossRefGoogle Scholar
  19. 19.
    Kuhnert C, Albert M, Breyer S et al (2006) Phase equilibrium in formaldehyde containing multicomponent mixtures: experimental results for fluid phase equilibria of (formaldehyde + (water or methanol) + methylal) and (formaldehyde + water + methanol + methylal) and comparison with predictions. Ind Eng Chem Res 45(14):5155–5164CrossRefGoogle Scholar
  20. 20.
    Wang L, Wu WT, Chen T et al (2014) Ion-exchange resin-catalyzed synthesis of polyoxymethylene dimethyl ethers: a practical and environmentally friendly way to diesel additive. Chem Eng Commun 201(5):709–717CrossRefGoogle Scholar
  21. 21.
    Schmitz N, Homberg F, Berje J et al (2015) Chemical equilibrium of the synthesis of poly(oxymethylene) dimethyl ethers from formaldehyde and methanol in aqueous solutions. Ind Eng Chem Res 54(25):6409–6417CrossRefGoogle Scholar
  22. 22.
    Wang F, Zhu GL, Li Z et al (2015) Mechanistic study for the formation of polyoxymethylene dimethyl ethers promoted by sulfonic acid-functionalized ionic liquids. J Mol Catal A 408:228–236CrossRefGoogle Scholar
  23. 23.
    Drunsel JO, Renner M, Hasse H (2012) Experimental study and model of reaction kinetics of heterogeneously catalyzed methylal synthesis. Chem Eng Res Des 90(5):696–703CrossRefGoogle Scholar

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

Authors and Affiliations

  1. 1.School of Chemical Engineering and TechnologyTianjin UniversityTianjinChina

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