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Post-treatment of TS-1 with Mixtures of TPAOH and Ammonium Salts and the Catalytic Properties in Propylene Epoxidation

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Abstract

TS-1/SiO2 extrudate was post-treated with mixed solution of tetrapropyl ammonium hydroxide (TPAOH) and various ammonium salts solution (NH4F, (NH4)3PO4, (NH4)2CO3, (NH4)2SO4, NH4CH3CO2, NH4NO3, NH4Cl and (NH4)2TiF6). The obtained hierarchical TS-1 catalysts were characterized by many techniques and tested for propylene epoxidation using hydrogen peroxide as an oxidant in a fixed-bed reactor. It was shown that the physicochemical and catalytic properties of the treated TS-1/SiO2 extrudate depended on the types of ammonium salts added. Compared to the treatment with TPAOH alone, the treatment with a mixed solution of TPAOH and some ammonium salts can greatly improve the catalytic properties of the treated TS-1/SiO2 extrudate. Some of these ammonium salts were favorable for the incorporation of titanium in the framework, and the beneficial effect depended on the types of ammonium salt. TS-1/SiO2 extrudate treated with a mixed solution of TPAOH and (NH4)3PO4 exhibited the highest catalyst stability in propylene epoxidation. Such catalytic property can be correlated to high crystallinity, more framework titanium, large specific surface area and large external surface area.

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References

  1. Nijhuis TA, Makkee M, Moulijn JA et al (2006) The production of propene oxide: catalytic processes and recent developments. Ind Eng Chem Res 45(10):3447–3459

    Article  Google Scholar 

  2. Prieto G, Schüth F (2015) The Yin and Yang in the development of catalytic processes: catalysis research and reaction engineering. Angew Chem Int Ed 54(11):3222–3239

    Article  Google Scholar 

  3. Russo V, Tesser R, Santacesaria E et al (2013) Chemical and technical aspects of propene oxide production via hydrogen peroxide (HPPO process). Ind Eng Chem Res 52(3):1168–1178

    Article  Google Scholar 

  4. Ishino M, Yamamoto J (2006) Propylene oxide manufacturing processes. Shokubai (Catalysts & Catalysis) 48(7): 511‒515 (in Japanese)

  5. Tullo A (2004) Dow’s southern petrochemical pole. Chem Eng News 82(49):15

    Article  Google Scholar 

  6. Edwards JK, Hutchings GJ (2008) Palladium and gold-palladium catalysts for the direct synthesis of hydrogen peroxide. Angew Chem Int Ed 47(48):9192–9198

    Article  Google Scholar 

  7. Campos-Martin JM, Blanco-Brieva G, Fierro JLG (2006) Hydrogen peroxide synthesis: an outlook beyond the anthraquinone process. Angew Chem Int Ed 45(42):6962–6984

    Article  Google Scholar 

  8. Clerici MG, Bellussi G, Romano U (1991) Synthesis of propylene oxide from propylene and hydrogen peroxide catalyzed by titanium silicalite. J Catal 129(1):159–167

    Article  Google Scholar 

  9. Feng X, Chen D, Zhou XG (2016) Thermal stability of TPA template and size-dependent selectivity of uncalcined TS-1 supported Au catalyst for propene epoxidation with H2 and O2. RSC Adv 6(50):44050–44056

    Article  Google Scholar 

  10. Feng X, Liu Y, Li Y et al (2016) Au/TS-1 catalyst for propene epoxidation with H2/O2: a novel strategy to enhance stability by tuning charging sequence. AIChE J 62(11):3963–3972

    Article  Google Scholar 

  11. Feng X, Duan X, Cheng H et al (2015) Au/TS-1 catalyst prepared by deposition–precipitation method for propene epoxidation with H2/O2: insights into the effects of slurry aging time and Si/Ti molar ratio. J Catal 325:128–135

    Article  Google Scholar 

  12. Prieto A, Palomino M, Díaz U et al (2016) One-pot two-step process for direct propylene oxide production catalyzed by bi-functional Pd(Au)@TS-1 materials. Appl Catal A 523:73–84

    Article  Google Scholar 

  13. Taramasso M, Perego G, Notari B (1983) Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides: US, 4,410,501 [P]. 1983-10-18

  14. Li CG, Lu YQ, Wu HH et al (2015) A hierarchically core/shell-structured titanosilicate with multiple mesopore systems for highly efficient epoxidation of alkenes. Chem Commun 51(80):14905–14908

    Article  Google Scholar 

  15. Du ST, Li F, Sun QM et al (2016) A green surfactant-assisted synthesis of hierarchical TS-1 zeolites with excellent catalytic properties for oxidative desulfurization. Chem Commun 52(16):3368–3371

    Article  Google Scholar 

  16. Wu XX, Wang YQ, Zhang T et al (2014) Effect of TS-1 treatment by tetrapropyl ammonium hydroxide on cyclohexanone ammoximation. Catal Commun 50:59–62

    Article  Google Scholar 

  17. Wang YQ, Wang SH, Zhang T et al (2017) Effect of extra-framework titanium in TS-1 on the ammoximation of cyclohexanone. Trans Tianjin Univ 23(3):230–236

    Article  Google Scholar 

  18. Wang YQ, Ye JX, Wang SH et al (2016) Synthesis of mesoporous titanium silicalite-1 with high stability in cyclohexanone ammoximation. Trans Tianjin Univ 22(3):254–260

    Article  Google Scholar 

  19. Clerici MG (2006) TS-1 and propylene oxide, 20 years later. Oil Gas European Magazine 122(6):77–82

    Google Scholar 

  20. Clerici MG, Ingallina P (1993) Epoxidation of lower olefins with hydrogen peroxide and titanium silicalite. J Catal 140:71–83

    Article  Google Scholar 

  21. Sanz R, Serrano DP, Pizarro P et al (2011) Hierarchical TS-1 zeolite synthesized from SiO2-TiO2 xerogels imprinted with silanized protozeolitic units. Chem Eng J 171(3):1428–1438

    Article  Google Scholar 

  22. Serrano DP, Sanz R, Pizarro P et al (2012) Tailoring the properties of hierarchical TS-1 zeolite synthesized from silanized protozeolitic units. Appl Catal A 435–436:32–42

    Article  Google Scholar 

  23. Yang ST, Jeong KE, Jeong SY et al (2012) Synthesis of mesoporous TS-1 using a hybrid SiO2-TiO2 xerogel for catalytic oxidative desulfurization. Mater Res Bull 47(12):4398–4402

    Article  Google Scholar 

  24. Serrano DP, Sanz R, Pizarro P et al (2013) Improvement of the hierarchical TS-1 properties by silanization of protozeolitic units in presence of alcohols. Microporous Mesoporus Mater 166:59–66

    Article  Google Scholar 

  25. Zhao ZL, Liu YM, Wu HH et al (2010) Hydrothermal synthesis of mesoporous titanosilicate with the aid of amphiphilic organosilane. J Porous Mat 17(4):399–408

    Article  Google Scholar 

  26. Serrano DP, Sanz R, Pizarro P et al (2014) Narrowing the mesopore size distribution in hierarchical TS-1 zeolite by surfactant-assisted reorganization. Microporous Mesoporus Mater 189:71–82

    Article  Google Scholar 

  27. Lee S, Shantz DF (2005) Zeolite growth in nonionic microemulsions: synthesis of hierarchically structured zeolite particles. Chem Mater 17(2):409–417

    Article  Google Scholar 

  28. Zuo Y, Liu M, Zhang T et al (2015) Enhanced catalytic performance of titanium silicalite-1 in tuning the crystal size in the range 1200–200 nm in a tetrapropylammonium bromide system. Chem Cat Chem 7(17):2660–2668

    Google Scholar 

  29. Fang YM, Hu HQ (2007) Mesoporous TS-1: nanocasting synthesis with CMK-3 as template and its performance in catalytic oxidation of aromatic thiophene. Catal Commun 8(5):817–820

    Article  Google Scholar 

  30. Xin HC, Zhao J, Xu ST et al (2010) Enhanced catalytic oxidation by hierarchically structured TS-1 zeolite. J Phys Chem C 114(14):6553–6559

    Article  Google Scholar 

  31. Choi M, Cho HS, Srivastava R et al (2006) Amphiphilic organosilane-directed synthesis of crystalline zeolite with tunable mesoporosity. Nature Mater 5(9):718–723

    Article  Google Scholar 

  32. Na K, Jo C, Kim J et al (2011) Directing zeolite structures into hierarchically nanoporous architectures. Science 333(6040):328–332

    Article  Google Scholar 

  33. Schwieger W, Machoke AG, Weissenberger T et al (2016) Hierarchy concepts: classification and preparation strategies for zeolite containing materials with hierarchical porosity. Chem Soc Rev 45(12):3353–3376

    Article  Google Scholar 

  34. Wang YR, Lin M, Tuel A (2007) Hollow TS-1 crystals formed via a dissolution–recrystallization process. Microporous Mesoporus Mater 102(1–3):80–85

    Article  Google Scholar 

  35. Lin M, Shu XT, Wang XQ et al. (2002) Titanium-silicalite molecular sieve and the method for its preparation: US, 6,475,465 [P]. 2002-11-05

  36. Silvestre-Albero A, Grau-Atienza A, Serrano E et al (2014) Desilication of TS-1 zeolite for the oxidation of bulky molecules. Catal Commun 44:35–39

    Article  Google Scholar 

  37. Wang BR, Lin M, Zhu B et al (2016) The synthesis, characterization and catalytic activity of the hierarchical TS-1 with the intracrystalline voids and grooves. Catal Commun 75:69–73

    Article  Google Scholar 

  38. Song W, Zuo Y, Xiong G et al (2014) Transformation of SiO2 in titanium silicalite-1/SiO2 extrudates during tetrapropylammonium hydroxide treatment and improvement of catalytic properties for propylene epoxidation. Chem Eng J 253(1):464–471

    Article  Google Scholar 

  39. Song W, Xiong G, Long H et al (2015) Effect of treatment with different bases on the catalytic properties of TS-1/SiO2 extrudates in propylene epoxidation. Microporous Mesoporus Mater 212:48–55

    Article  Google Scholar 

  40. Wang YQ, Liu W, Lin YJ et al (2016) Effects of the amount of tetrapropyl ammonium hydroxide in synthesis on TS-1 properties and catalytic performance in epoxidation of propylene. Trans Tianjin Univ 22(5):458–465

    Article  Google Scholar 

  41. Xu J, Wang YQ, Feng WP et al (2014) Effect of triethylamine treatment of titanium silicalite-1 on propylene epoxidation. Front Chem Sci Eng 8(4):478–487

    Article  Google Scholar 

  42. Wang YQ, Li HY, Liu W et al (2018) Effect of TS-1 treatment by mixed alkaline on propylene epoxidation. Trans Tianjin Univ 24(1):25–31

    Article  Google Scholar 

  43. Feng WP, Wang YQ, Wu GQ et al (2015) Liquid phase propylene epoxidation with H2O2 on TS-1/SiO2 catalyst in a fixed-bed reactor: experiments and deactivation kinetics. J Chem Technol Biotechnol 90(8):1489–1496

    Article  Google Scholar 

  44. Wu GQ, Wang YQ, Wang LN et al (2013) Epoxidation of propylene with H2O2 catalyzed by supported TS-1 catalyst in a fixed-bed reactor: experiments and kinetics. Chem Eng J 215–216:306–314

    Article  Google Scholar 

  45. Deng XJ, Zhang S, Wang BS et al (2013) Enhanced catalytic activity of titanosilicates controlled by hydrogen-bonding interactions. Chem Commun 49(68):7504–7506

    Article  Google Scholar 

  46. Schumb WC, Satterfield CN, Wentworth RL (1955) Hydrogen Peroxide. Reinhold, New York

    Google Scholar 

  47. Fang XQ, Wang Q, Zheng A et al (2013) Post-synthesis, characterization and catalytic properties of fluorine-planted MWW-type titanosilicate. Phys Chem Chem Phys 15(14):4930–4938

    Article  Google Scholar 

  48. Jiao K, Xu XY, Lv Z et al (2016) Synthesis of nanosized silicalite-1 in F-media. Microporous Mesoporus Mater 225:98–104

    Article  Google Scholar 

  49. Wang L, Wang F, Wang JD (2016) Non-mercury catalytic acetylene hydrochlorination over a NH4F-urea-modified Pd/HY catalyst for vinyl chloride monomer production. New J Chem 40(4):3019–3023

    Article  Google Scholar 

  50. Meng FJ, Wang YQ, Wang SH (2016) Methanol to gasoline over zeolite ZSM-5: improved catalyst performance by treatment with HF. RSC Adv 6(63):58586–58593

    Article  Google Scholar 

  51. Goa Y, Wu P, Tatsumi T (2004) Influence of fuorine on the catalytic performance of Ti-Beta zeolite. J Phys Chem B 108(14):4242–4244

    Article  Google Scholar 

  52. Fan WB, Fan BB, Shen XH et al (2009) Effect of ammonium salts on the synthesis and catalytic properties of TS-1. Microporous Mesoporus Mater 122(1–3):301–308

    Article  Google Scholar 

  53. Fan WB, Duan RG, Yokoi T et al (2008) Synthesis, crystallization mechanism, and catalytic properties of titanium-rich TS-1 free of extraframework titanium species. J Am Chem Soc 130(31):10150–10164

    Article  Google Scholar 

  54. Lamberti C, Bordiga S, Zecchina A et al (2001) Ti location in the MFI framework of Ti-silicalite-1: a neutron powder diffraction study. J Am Chem Soc 123(10):2204–2212

    Article  Google Scholar 

  55. Bordiga S, Bonino F, Damin A et al (2007) Reactivity of Ti(iv) species hosted in TS-1 towards H2O2-H2O solutions investigated by ab initio cluster and periodic approaches combined with experimental XANES and EXAFS data: a review and new highlights. Phys Chem Chem Phys 9(35):4854–4878

    Article  Google Scholar 

  56. Marra GL, Tozzola G, Leofanti G et al (1994) Orthorhombic and monoclinic silicalites: structure, morphology, vibrational properties and crystal defects. Stud Surf Sci Catal 84:559–566

    Article  Google Scholar 

  57. Zuo Y, Liu M, Hong L et al (2015) Role of supports in the tetrapropylammonium hydroxide treated titanium silicalite-1 extrudates. Ind Eng Chem Res 54(5):1513–1519

    Article  Google Scholar 

  58. Wilde N, Pelz M, Gebhardt SG et al (2015) Highly efficient nano-sized TS-1 with micro-/mesoporosity from desilication and recrystallization for the epoxidation of biodiesel with H2O2. Green Chem 17(6):3378–3389

    Article  Google Scholar 

  59. Ge TG, Hua ZL, Lv J et al (2017) Hydrophilicity/hydrophobicity modulated synthesis of nano-crystalline and hierarchically structured TS-1 zeolites. Cryst Eng Comm 19(10):1370–1376

    Article  Google Scholar 

  60. Shan ZC, Lu ZD, Wang L et al (2010) Stable bulky particles formed by TS-1 zeolite nanocrystals in the presence of H2O2. Chem Cat Chem 2(4):407–412

    Google Scholar 

  61. Zhou J, Hua ZL, Cui XZ et al (2010) Hierarchical mesoporous TS-1 zeolite: a highly active and extraordinarily stable catalyst for the selective oxidation of 2,3,6-trimethylphenol. Chem Commun 46(27):4994–4996

    Article  Google Scholar 

  62. Blasco T, Camblor MA, Corma A et al (1993) The State of Ti in titanoaluminosilicates isomorphous with zeolite β. J Am Chem Soc 115:11806–11813

    Article  Google Scholar 

  63. Qiu FR, Wang XB, Zhang XF et al (2009) Preparation and properties of TS-1 zeolite and film using Sil-1 nanoparticles as seeds. Chem Eng J 147(2–3):316–322

    Article  Google Scholar 

  64. Jansen JC, van der Gaag FJ, van Bekkum H (1984) Identification of ZSM-type and other 5-ring containing zeolites by i.r. spectroscopy. Zeolites 4(4):369‒372

  65. Jacobs PA, Beyer HK, Valyon J (1981) Properties of the end members in the pentasil-family of zeolites: characterization as adsorbents. Zeolites 1(3):161–168

    Article  Google Scholar 

  66. Wang ZD, Xu L, Jiang JG et al (2012) One-pot synthesis of catalytically active and mechanically robust mesoporous TS-1 microspheres with the aid of triblock copolymer. Microporous Mesoporus Mater 156:106–114

    Article  Google Scholar 

  67. Ricchiardi G, Damin A, Bordiga S et al (2001) Vibrational structure of titanium silicate catalysts. A spectroscopic and theoretical study. J Am Chem Soc 123(46):11409–11419

    Article  Google Scholar 

  68. Thangaraj A, Kumar R, Mirajkar SP et al (1991) Catalytic properties of crystalline titanium silicalites I. Synthesis and characterization of titanium-rich zeolites with MFI structure. J Catal 130(1):1–8

    Article  Google Scholar 

  69. Thangaraj A, Sivasanker S (1992) An improved method for TS-1 synthesis: 29Si NMR studies. J Chem Soc Chem Commun 2:123–124

    Article  Google Scholar 

  70. Wilde N, Přech J, Pelz M et al (2016) Accessibility enhancement of TS-1-based catalysts for improving the epoxidation of plant oil-derived substrates. Catal Sci Technol 6(19):7280–7288

    Article  Google Scholar 

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Acknowledgements

This work was supported by National Natural Science Foundation of China (No. 21276183).

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Authors and Affiliations

  1. Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300350, China

    Yaquan Wang, Xinpeng Han, Haoyang Li & Xiao Wang

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  1. Yaquan Wang
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  2. Xinpeng Han
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  4. Xiao Wang
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Correspondence to Yaquan Wang.

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Wang, Y., Han, X., Li, H. et al. Post-treatment of TS-1 with Mixtures of TPAOH and Ammonium Salts and the Catalytic Properties in Propylene Epoxidation. Trans. Tianjin Univ. 24, 461–470 (2018). https://doi.org/10.1007/s12209-018-0134-x

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