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Hydroxylation of phenol with H2O2 over binary Cu–Pd–alginate catalyst in the fixed-bed flow reactor

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Abstract

A series of Cu–alginate and Cu–Pd–alginate catalysts were prepared by the ion exchange of Na–alginate, and their structures were well characterized by FT-IR, XPS and ICP-AES measurements. Their catalytic activities for phenol hydroxylation in the fixed-bed flow reactor were investigated. The effects of different reaction conditions, such as molar ratio of phenol/H2O2, reaction temperature, weight hourly space velocity, solution and weight ratio of water/phenol were evaluated. Under the optimum reaction conditions, 17.1 % phenol conversion was obtained with selectivities to catechol and hydroquinone being 67.7 and 31.4 %, respectively. The 16.0–18.0 % phenol conversion and selectivities to HQ 30.0–32.0 %, CAT 66.0–68.0 % and BQ 0.7–2.0 % of the long-run catalytic test confirmed the excellent stable catalytic activity of the catalyst.

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References

  1. Jian LJ, Chen C, Lan F, Deng SJ, Xiao WM, Zhang N (2011) Catalytic activity of unsaturated coordinated Cu-MOF to the hydroxylation of phenol. Solid State Sci 13:1127–1131

    Article  Google Scholar 

  2. Mugo JN, Mapolie SF, Wyk JL (2010) Cu (II) and Ni (II) complexes based on monofunctional and dendrimeric pyrrole-imine ligands: applications in catalytic liquid phase hydroxylation of phenol. Inorg Chim Acta 363:2643–2651

    Article  CAS  Google Scholar 

  3. Wu G, Tan XY, Li GY, Hu CW (2010) Effect of preparation method on the physical and catalytic property of nanocrystalline Fe2O3. J Alloys Comp 504:371–376

    Article  CAS  Google Scholar 

  4. Ray S, Mapolie SF, Darkwa J (2007) Catalytic hydroxylation of phenol using immobilized late transition metal salicylaldimine complexes. J Mol Catal A Chem 267:143–148

    Article  CAS  Google Scholar 

  5. Zhang GY, Long JL, Wang XX, Zhang ZZ, Dai WX, Liu P, Li ZH, Wu L, Fu XZ (2010) Catalytic Role of Cu Sites of Cu/MCM-41 in phenol hydroxylation. Langmuir 26:1362–1371

    Article  CAS  Google Scholar 

  6. Abbo HS, Titinchi SJJ (2010) Synthesis and catalytic activity of Cu (II), Fe(III) and Bi(III) complexes of thio-schiff base encapsulated in zeolite-Y for hydroxylation of phenol. Top Catal 53:254–264

    Article  CAS  Google Scholar 

  7. Mirica LM, Vance M, Rudd DJ, Hedman B, Hodgson KO, Solomon EI, Stack TDP (2005) Tyrosinase reactivity in a model complex: an alternative hydroxylation mechanism. Science 308:1890–1892

    Article  CAS  Google Scholar 

  8. Palavicini S, Granata A, Monzani E, Casella L (2005) Hydroxylation of phenolic compounds by a peroxodicopper (II) complex: further insight into the mechanism of tyrosinase. J Am Ceram Soc 127:18031–18036

    CAS  Google Scholar 

  9. Yang JS, Xie YJ, Wen H (2011) Research progress on chemical modification of alginate: a review. Carbohydr Polym 84:33–39

    Article  CAS  Google Scholar 

  10. Stokke BT, Smidsrød O, Bruheim P, Skjak-Bræk G (1991) Distribution of uronate residues in alginate chains in relation to alginate gelling properties. Macromolecules 24:4637–4645

    Article  CAS  Google Scholar 

  11. Torres E, Mata YN, Blázquez ML, Munoz JA, González F, Ballester A (2005) Gold and silver uptake and nanoprecipitation on calcium alginate beads. Langmuir 21:7951–7958

    Article  CAS  Google Scholar 

  12. Grace M, Chand N, Bajpai SK (2009) Copper alginate-cotton cellulose (CACC) fibers with excellent antibacterial properties. J Eng Fiber Fabr 4:24–35

    CAS  Google Scholar 

  13. Kong HJ, Kaigler D, Kim K, Mooney DJ (2004) Controlling rigidity and degradation of alginate hydrogels via molecular weight distribution. Biomacromolecules 5:1720–1727

    Article  CAS  Google Scholar 

  14. Gomez CG, Rinaudo M, Villar MA (2007) Oxidation of sodium alginate and characterization of the oxidized derivatives. Carbohydr Polym 67:296–304

    Article  CAS  Google Scholar 

  15. Wong TW (2011) Alginate graft copolymers and alginate-co-excipient physical mixture in oral drug delivery. J Pharm Pharmacol 63:1497–1512

    Article  CAS  Google Scholar 

  16. Laurienzo P, Malinconico M, Motta A, Vicinanza A (2005) Synthesis and characterization of a novel alginate–poly (ethylene glycol) graft copolymer. Carbohydr Polym 62:274–282

    Article  CAS  Google Scholar 

  17. Alban S, Schauerte A, Franz G (2002) Anticoagulant sulfated polysaccharides: part I. Synthesis and structure- activity relationships of new pullulan sulfates. Carbohydr Polym 47:267–276

    Article  CAS  Google Scholar 

  18. Park JN, Wang J, Choi KY, Dong WY, Hong SI, Lee CW (2006) Hydroxylation of phenol with H2O2 over Fe2+ and/or Co2+ ion-exchanged NaY catalyst in the fixed-bed flow reactor. J Mol Catal A Chem 247:73–79

    Article  CAS  Google Scholar 

  19. Liu H, Lu GZ, Guo YL, Guo Y (2005) Synthesis of TS-1 using amorphous SiO2 and its catalytic properties for hydroxylation of phenol in fixed-bed reactor. Appl Catal A 293:153–161

    Article  CAS  Google Scholar 

  20. Tendulkar SB, Tambe SS, Chandra I, Rao PV, Naik RV, Kulkarni BD (1998) Hydroxylation of phenol to dihydroxybenzenes: development of artificial neural-network-based process identification and model predictive control strategies for a pilot plant scale reactor. Ind Eng Chem Res 37:2081–2085

    Article  CAS  Google Scholar 

  21. Liu H, Lu GZ, Guo YL, Guo Y, Wang JS (2006) Chemical kinetics of hydroxylation of phenol catalyzed by TS-1/diatomite in fixed-bed reactor. Chem Eng J 116:179–186

    Article  CAS  Google Scholar 

  22. Shams K, Najari S (2011) Dynamics of intraparticle desorption and chemical reaction in fixed-beds using inert core spherical particles. Chem Eng J 172:500–506

    Article  CAS  Google Scholar 

  23. Iliuta I, Thyrion FC, Muntean O, Giot M (1996) Residence time distribution of the liquid in gas-liquid cocurrent upflow fixed-bed reactors. Chem Eng Sci 50:4579–4593

    Article  Google Scholar 

  24. Bucalá V, Borio DO, Porras J (1997) Thermal regimes in cocurrently cooled fixed-bed reactors for parallel reactions: application to practical design problems. Chem Eng Sci 52:1577–1587

    Article  Google Scholar 

  25. Dixon AG, Walls G, Stanness H, Nijemeisland M, Stitt EH (2012) Experimental validation of high Reynolds number CFD simulations of heat transfer in a pilot-scale fixed bed tube. Chem Eng J 200–202:344–356

    Article  Google Scholar 

  26. Shi FW, Chen YG, Sun LP, Zhang L, Hu JL (2012) Hydroxylation of phenol catalyzed by different forms of Cu-alginate with hydrogen peroxide as an oxidant. Catal Commun 25:102–105

    Article  CAS  Google Scholar 

  27. Shi FW, Zheng JL, Xu K, Zhang L, Hu JL (2012) Synthesis of binary Cu–Pd–alginates dry bead and its high catalytic activity for hydroxylation of phenol. Catal Commun 28:23–26

    Article  CAS  Google Scholar 

  28. Papageorgiou SK, Kouvelos EP, Favvas EP, Sapalidis AA, Romanos GE, Katsaros FK (2010) Metal–carboxylate interactions in metal–alginate complexes studied with FTIR spectroscopy. Carbohydr Res 345:469–473

    Article  CAS  Google Scholar 

  29. Jiang YJ, Gao QM (2007) Preparation of Cu2+/+–VSB-5 and their catalytic properties on hydroxylation of phenol. Mater Lett 61:2212–2216

    Article  CAS  Google Scholar 

  30. Rodrigues A, Costa P, Méthivier C, Dzwigaj S (2011) Controlled preparation of CoPdSiBEA zeolite catalysts for selective catalytic reduction of NO with methane and their characterisation by XRD, DR UV–Vis, TPR, XPS. Catal Today 176:72–76

    Article  CAS  Google Scholar 

  31. Clerici MG, Bellussi G, Romano U (1991) Synthesis of propylene oxide from propylene and hydrogen peroxide catalyzed by titanium silicalite. J Catal 129:159–167

    Article  CAS  Google Scholar 

  32. Yadav GD, Pujari AA (2000) Epoxidation of styrene to styrene oxide: synergism of heteropoly acid and phase-transfer catalyst under ishii-venturello mechanism. Org Process Res Dev 4:88–93

    Article  CAS  Google Scholar 

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Acknowledgments

This work was supported by the Natural Science Fund Council of China (21203013) and Undergraduate Scientific and Technological Innovation Project of Changchun University of Technology (2014cxcy156). The authors gratefully acknowledge the Centre of Analysis and Testing of Northeast Normal University and Changchun University of Technology for all of the support that was provided.

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Authors and Affiliations

  1. School of Chemical Engineering, Changchun University of Technology, Changchun, People’s Republic of China

    Fengwei Shi, Yingying Luo, Wei Wang, Jianglei Hu & Long Zhang

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  1. Fengwei Shi
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  2. Yingying Luo
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  4. Jianglei Hu
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  5. Long Zhang
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Correspondence to Long Zhang.

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Shi, F., Luo, Y., Wang, W. et al. Hydroxylation of phenol with H2O2 over binary Cu–Pd–alginate catalyst in the fixed-bed flow reactor. Reac Kinet Mech Cat 115, 187–199 (2015). https://doi.org/10.1007/s11144-015-0836-1

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  • DOI: https://doi.org/10.1007/s11144-015-0836-1

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