Reaction Kinetics, Mechanisms and Catalysis

, Volume 128, Issue 1, pp 461–477 | Cite as

Stabilized hydrogenolysis of glycerol to 1,3-propanediol over Mg modified Pt/WOx–ZrO2 catalysts

  • Chao Wang
  • Changlin ChenEmail author


Stable hydrogenolysis of glycerol to value-added 1,3-propanediol (1,3-PDO) over WOx-containing catalyst is a serious challenge in aqueous solution. Because the tungsten oxide can interact with the H+ to form H2WO4 and dissolve to deactivate for catalyst under hydrothermal condition. Therefore, we prepared stable Pt/WOx–ZrO2 catalysts modified with Mg by the method of impregnation–calcination. The Raman and H2-TPR spectra demonstrate that the polymerization degree of WOx on the catalyst surface could be effectively reduced by introducing Mg. The formation of smaller WOx species are conducive to the formation of 1,3-PDO. Among them, the Pt/0.66Mg/WOx–ZrO2 achieved the maximum 62.4% selectivity of 1,3-PDO. In addition, the Pt/WOx–ZrO2 catalyst was deactivated due to leaching of tungsten from ZrO2 surface into the aqueous solution. Introduction of Mg can inhibit the leaching of tungsten and greatly improve the stability in hydrogenolysis of glycerol. So the Pt/0.50Mg/WOx–ZrO2 catalyst showed excellent stability with 56% conversion and 33% yield of 1,3-PDO under an extremely long 400 h time-on-stream.


Glycerol hydrogenolysis 1,3-Propanediol Magnesium Polytungstate Stability 



Financial support by the Research and Development of Prospective Research Project of Jiangsu Province, China (BY2015005-08) is gratefully acknowledged.


  1. 1.
    Zhou CC, Beltramini JN, Fan YX, Lu GQ (2008) Chem Soc Rev 37:527–549CrossRefGoogle Scholar
  2. 2.
    Behr A, Eilting J, Irawadi K, Leschinski J, Lindner F (2008) Green Chem 10:13–30CrossRefGoogle Scholar
  3. 3.
    Xie QL, Li SS, Gong RC, Zheng GJ, Wang YL, Xu P, Duan Y, Yu SZ, Lu MZ, Ji WR, Nie Y, Ji JB (2019) Appl Catal B: Environ 243:455–462CrossRefGoogle Scholar
  4. 4.
    Sullivan JA, Burnham S (2014) Catal Commun 56:72–75CrossRefGoogle Scholar
  5. 5.
    Kong PS, Aroua MK, Daud WMAW (2015) Rev Chem Eng 31:437–451CrossRefGoogle Scholar
  6. 6.
    Nimlos MR, Blanksby SJ, Qian X, Himmel ME, Johnson DK (2006) J Phys Chem A 110:6145–6156CrossRefGoogle Scholar
  7. 7.
    Yue HR, Zhao YJ, Ma XB, Gong JL (2012) Chem Soc Rev 41:4218–4244CrossRefGoogle Scholar
  8. 8.
    Shi GJ, Cao Z, Xu JY, Jin K, Bao Y, Xu SH (2018) Catal Lett 148:2304–2314CrossRefGoogle Scholar
  9. 9.
    Li C, He B, Ling Y, Tsang CW, Liang CH (2018) Chin J Catal 39:1121–1128CrossRefGoogle Scholar
  10. 10.
    Priya SS, Kumar VP, Kantam ML, Bhargava SK, Srikanth A, Chary KVR (2015) Ind Eng Chem Res 54:9104–9115CrossRefGoogle Scholar
  11. 11.
    Pamphile-Adrián AJ, Florez-Rodriguez PP, Pires MHM, Perez G, Passos FB (2017) Catal Today 289:302–308CrossRefGoogle Scholar
  12. 12.
    Deng CH, Leng LL, Duan XZ, Zhou JG, Zhou XG, Yuan WK (2015) J Mol Catal A-Chem 410:81–88CrossRefGoogle Scholar
  13. 13.
    Shi GJ, Xu JY, Song ZG, Cao Z, Jin K, Xu SH, Yan XT (2018) Mol Catal 456:22–30CrossRefGoogle Scholar
  14. 14.
    García-Fernández S, Gandarias I, Requies J, Soulimani F, Arias PL, Weckhuysen BM (2017) Appl Catal B 204:260–272CrossRefGoogle Scholar
  15. 15.
    Feng SH, Zhao BB, Liu L, Dong JX (2017) Ind Eng Chem Res 56:11065–11074CrossRefGoogle Scholar
  16. 16.
    Zhang YH, Zhao XC, Wang Y, Zhou LK, Zhang JY, Wang J, Wang AQ, Zhang T (2013) J Mater Chem A 1:3724–3732CrossRefGoogle Scholar
  17. 17.
    Kurosaka T, Maruyama H, Naribayashi I, Sasaki Y (2008) Catal Commun 9:1360–1363CrossRefGoogle Scholar
  18. 18.
    Qin LZ, Song MJ, Chen CL (2010) Green Chem 12:1466–1472CrossRefGoogle Scholar
  19. 19.
    Garcia-Fernandez S, Gandarias I, Tejido-Nunez Y, Requies J, Arias PL (2017) ChemCatChem 24:4508–4519CrossRefGoogle Scholar
  20. 20.
    Zhou W, Luo J, Wang Y, Liu JF, Zhao YJ, Wang SP, Ma XB (2019) Appl Catal B 242:410–421CrossRefGoogle Scholar
  21. 21.
    Cortés-Jácome MA, Angeles-Chavez C, López-Salinas E, Navarrete J, Toribio P, Toledo JA (2007) Appl Catal A 318:178–189CrossRefGoogle Scholar
  22. 22.
    Zhu SH, Gao XQ, Zhu YL, Cui JL, Zheng HY, Li YW (2014) Appl Catal B 158–159:391–399CrossRefGoogle Scholar
  23. 23.
    Fabičovicová K, Lucas M, Claus P (2015) Green Chem 17:3075–3083CrossRefGoogle Scholar
  24. 24.
    Lucas M, Fabicovicova K, Claus P (2018) ChemCatChem 10:612–618CrossRefGoogle Scholar
  25. 25.
    Zhu SH, Gao XQ, Zhu YL, Zhu YF, Xiang XM, Hu CX, Li YW (2013) Appl Catal B 140:60–67CrossRefGoogle Scholar
  26. 26.
    Zhu M, Chen CL (2018) Reac Kinet Mech Cat 124:683–699CrossRefGoogle Scholar
  27. 27.
    Gu MY, Shen Z, Yang L, Peng BY, Dong WJ, Zhang W, Zhang YL (2017) Ind Eng Chem Res 56:13572–13581CrossRefGoogle Scholar
  28. 28.
    Mohandes F, Davar F, Salavati-Niasari M (2010) J Phys Chem Solids 71:1623–1628CrossRefGoogle Scholar
  29. 29.
    Selvam NCS, Kumar RT, Kennedy LJ, Vijaya JJ (2011) J Alloy Compd 509:9809–9815CrossRefGoogle Scholar
  30. 30.
    López DE, Suwannakarn K, Bruce DA Jr, Goodwin JG Jr (2007) J Catal 247:43–50CrossRefGoogle Scholar
  31. 31.
    Kourieh R, Bennici S, Marzo M, Gervasini A, Auroux A (2012) Catal Commun 19:119–126CrossRefGoogle Scholar
  32. 32.
    Scheithauer M, Grasselli RK, Knozinger H (1998) Langmuir 14:3019–3029CrossRefGoogle Scholar
  33. 33.
    Song KS, Zhang HB, Zhang YH, Tang Y, Tang KJ (2013) J Catal 299:119–128CrossRefGoogle Scholar
  34. 34.
    Zhu SH, Gao XQ, Zhu YL, Li YW (2015) J Mol Catal A 398:391–398CrossRefGoogle Scholar
  35. 35.
    Niu L, Wei RP, Li C, Gao LJ, Zhou MH, Jiang F, Xiao GM (2015) Reac Kinet Mech Cat 115:377–388CrossRefGoogle Scholar
  36. 36.
    Geng GL, Wei RP, Liang T, Zhou MH, Xiao GM (2016) Reac Kinet Mech Cat 117:239–251CrossRefGoogle Scholar
  37. 37.
    Wang AQ, Zhang T (2013) Accounts Chem Res 46:1377–1386CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2019

Authors and Affiliations

  1. 1.State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical EngineeringNanjing Tech UniversityNanjingChina

Personalised recommendations