4.6 Article

Novel aluminophosphate (AlPO) bound ZSM-5 extrudates with improved catalytic properties for methanol to propylene (MTP) reaction

Journal

APPLIED CATALYSIS A-GENERAL
Volume 374, Issue 1-2, Pages 18-25

Publisher

ELSEVIER
DOI: 10.1016/j.apcata.2009.11.019

Keywords

Aluminophosphate; ZSM-5; Acidity control; Mechanical strength; MTP

Funding

  1. Korea Ministry of Knowledge Economy (MKE)
  2. Korea Federation of Science & Technology (KOSEF)

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Novel aluminophosphate (AlPO) binders consisting of dense phases of alpha-cristobalite and tridymite were prepared by the treatment of pseudo-boehmite (AlO(OH)) with phosphoric acid. The ZSM-5 extrudates prepared by using AlPO binders have been characterized by XRD, N-2 sorption, NH3-TPD Al-27 and P-31 NMR techniques to elucidate the changes that occurred in the textural properties of the catalyst and their implications on the catalytic activity of the resultant ZSM-5-based extrudates towards methanol to propylene (MTP) reaction. XRD indicated the chemical interaction of P with the alumina binder to form a highly dense crystalline phase of aluminophosphate, alpha-cristobalite. N-2 adsorption. while NH3-TPD studies revealed the changes in pore morphology of AlO(OH) binder and acidity of ZSM-5 in phosphorus containing extrudates. The drastic decrease in mesoporosity of the AlO(OH) observed after phosphorus addition indeed envisions the disappearance of inter-crystalline voids in the AlO(OH), probably due to a change in its morphology from the crystalline phase to amorphous AlPO phase. Al-27 and P-31 NMR studies further confirmed the formation of AlPO in these samples. The resultant ZSM-5-based extrudates exhibited enhanced properties of hydrothermal stability, mechanical strength, propylene yield and coke resistance in methanol to propylene (MTP) reaction. The positive aspect of P addition was continuously increased with P amount; at optimum P/Al (binder) ratio of similar to 0.8, the catalyst exhibited about 80% yield to C-2-C-4 olefins with the major component being propylene (similar to 50%) at near 100% methanol conversion. The catalyst also exhibited the stable performance in the studied period of 150 h. (c) 2009 Elsevier B.V. All rights reserved.

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