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Synthesis and Characterization of Aluminophosphates Type-5 and 36 Doubly Modified with Si and Zn and Its Catalytic Application in the Reaction of Methanol to Hydrocarbons (MTH)

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Abstract

This paper presents a study of the synthesis of AlPO4-5 and AlPO4-36 materials doubly substituted by Si and Zn, as acid function and aromatizing function, respectively. The physicochemical properties of the zeotypes were studied by XRD, adsorption of N2, Temperature Programmed Desorption with NH3, 31P MAS NMR and SEM. The incorporation of Zn and Si has shown an important effect on the acidic, textural and morphological properties of the samples. The particle size has a significant effect on the catalytic activity in the reaction of methanol to hydrocarbons in terms of methanol conversion and selectivity. It was observed that as the particle size decreases, the methanol conversion increases causing the catalyst to deactivate in a shorter time. The incorporation of Zn improved the selectivity to total aromatics by the aromatizing effect of Zn. The SAPO-5 (S5) material having a smaller particle size showed complete conversions of methanol. In contrast, the ZnAPO-5 (Z5) material showed low conversions but a high selectivity to total aromatics (41%). On the other hand, the material S36-2 presented a high selectivity to aromatics (58%) due to the high amount of Zn and Si. Both metals provided a certain acidic character to the materials.

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Abbreviations

MTH:

Methanol to hydrocarbons

MTA:

Methanol to aromatics

MTO:

Methanol to olefins

AlPO4-n:

Microporous crystalline aluminophosphate

MeAPO:

Microporous crystalline aluminophosphate containing a transition metal ion

MeAPSO:

Microporous crystalline aluminophosphate doubly substituted by two transition metal iones

BTX:

Bencene, toluene and xilenes fraction

AFI:

Aluminophosphate five structure

TRI:

Tridymite structure

ATS:

Aluminophosphate thirty-six structure

MCHA:

N-Methyldicyclohexylamine

TPA:

Tripropylamine

WHSV:

Weight hourly space velocity

SEM:

Scanning electron microscopy

ICP-OES:

Inductively coupled plasma optical emission spectrometry

NMR:

Nuclear magnetic resonance

BET:

Brunauer–Emmett–Teller equation

SM:

Substitution isomorphic

XRD:

X-ray diffraction

TPD:

Temperature programmed desorption

TGA:

Thermogravimetric analyses

DTG:

Derivate thermogravimetric

SDA:

Structure-directing agent

MR:

Member rings

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Acknowledgements

The authors thank the Spanish Research Agency -AEI- and the European Regional Development Fund -FEDER- for the financing of this work, through the Project MAT2016-77496-R (AEI / FEDER, EU). MGR thanks the Molecular Sieve Group of the Institute of Catalysis and Petrochemistry (CSIC) in Madrid and CONACyT for the support granted for the research stay in Spain. I thank Dr. Massiot for the ease of having the admfit program and doing the NMR deconvolution process to make the necessary calculations.

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Authors and Affiliations

  1. Doctorado en Ciencia de Materiales de La Facultad de Química, Universidad Autónoma del Estado de México, Paseo Colón Esquina Paseo Tollocan S/N, C.P. 50000, Toluca Estado de México, Mexico

    Misael García Ruiz

  2. Universidad Autónoma del Estado de México, Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Personal Académico Adscrito a La Facultad de Química, UAEMex, Toluca de Lerdo, Mexico

    Dora A. Solís Casados

  3. Área de Química Aplicada, Departamento de Ciencias Básicas, UAM-A, San pablo 180, C.P. 02200, Mexico, Mexico

    Julia Aguilar Pliego

  4. Instituto de Catálisis Y Petroleoquímica, CSIC, C/Marie Curie 2, Campus Cantoblanco, 28049, Madrid, Spain

    Carlos Márquez Álvarez, Enrique Sastre de Andrés, Diana Sanjurjo Tartalo, Manuel Sanchez-Sanchez & Marisol Grande Casas

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  1. Misael García Ruiz
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Contributions

All authors contributed to the study conception and design. Material preparation, data collection and analysis were performed by DASC (supervision), JAP (writing—review and editing), CMÁ (methodology), ESA (supervision), DST (investigation), MS-S and MGC (methodology). The first draft of the manuscript was written by PhD student, MGR and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript. We considerate the submitted is original and unique work and it has not been submitted to another journal simultaneity. The work is single study and it’s not up into several parts and results are presented clearly, honestly, and without, falsification or inappropriate the data manipulation, the study submitted is part of my doctoral thesis.

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Correspondence to Misael García Ruiz.

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García Ruiz, M., Solís Casados, D., Aguilar Pliego, J. et al. Synthesis and Characterization of Aluminophosphates Type-5 and 36 Doubly Modified with Si and Zn and Its Catalytic Application in the Reaction of Methanol to Hydrocarbons (MTH). Top Catal 63, 437–450 (2020). https://doi.org/10.1007/s11244-020-01266-3

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