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Transformation of Methanol to Hydrocarbons (MTH): Comparison Between MeAPO-36 (Me = Zn, Co, Mg) and Modified ZSM-5 Catalysts

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Abstract

This paper presents a study of the use of zeolitic catalysts and modified zeotypes for the reaction of transformation of methanol to hydrocarbons (MTH). Materials of the aluminophosphate type MeAPO-36 where Me is Zn, Mg and Co were prepared, in addition to modifying an acidic commercial zeolite with zinc ions by ion exchange. The physicochemical properties of the zeotypes were studied using XRD (X-ray diffraction), N2 adsorption–desorption, temperature programmed desorption of NH3 and SEM (Scanning Electron Microscopy). The catalytic performance of these catalysts was studied in the MTO reaction at 400 °C and atmospheric pressure using a WHSV of 4.24 h−1 in a fixed bed reactor. The incorporation of Zn in the ZSM-5 zeolite induced a relevant effect on acidity, generating a higher density of acid sites. In this sense, Zn-modified ZSM-5 showed higher selectivity to the BTX fraction (benzene, toluene and xylenes). The commercial zeolite modified with Zn ions presented a complete conversion of methanol with a higher selectivity of aromatics compounds totals (34.9% mol) at 400 °C. On the other hand, the incorporation of metals (Zn, Co, Mg) in MeAPO-36 materials had an important effect on acidity and therefore on selectivity in the MTH process. The olefins and paraffins selectivity decreased in the order Zn < Co ≈ Mg, being the selectivity to olefins close to 71–73% mol with these two latter catalysts, probably due to their low acidity. On the other hand, the ZnAPO-36 material was selective for the formation of aromatic compounds, due to the presence of zinc, which is an aromatizing agent.

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Abbreviations

AlPO4-n:

Microporous crystalline aluminophosphate

AFI:

Aluminophosphate five structure

ATS:

Aluminophosphate thirty-six structure

BET:

Brunauer – Emmett – Teller equation

BTX:

Bencene, toluene and xilenes fraction

DTG:

Derivate thermogravimetric

ICP-OES:

Inductively coupled plasma optical emission spectrometry

MR:

Member rings

MTA:

Methanol to aromatics

MTH:

Methanol to hydrocarbons

MTO:

Methanol to olefins

MeAPO:

Microporous crystalline aluminophosphate containing a transition metal ion,

SM:

Substitution isomorphic

SDA:

Structure-directing agent

SEM:

Scanning electron microscopy

TGA:

Thermogravimetric analyses

TPA:

Tripropylamine

TPD:

Temperature programmed desorption

WHSV:

Weight hourly space velocity

XRD:

X-ray diffraction

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Acknowledgements

The authors thank Comecyt—Consejo Mexiquense de Ciencia y Tecnología for catedra support. The authors thank the Spanish Research Agency -AEI- and the European Regional Development Fund—FEDER- for the funding of this work, through the Project MAT2016-77496-R funded by MCIN/AEI/http://dx.doi.org/10.13039/501100011033. MGR thanks the Molecular Sieves Group of the Institute of Catalysis and Petrochemistry (CSIC) in Madrid.

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Authors and Affiliations

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

    Misael García Ruiz & Dora A. Solís Casados

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

    Julia Aguilar Pliego

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

    Carlos Márquez Álvarez & Enrique Sastre de Andrés

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  1. Misael García Ruiz
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Correspondence to Misael García Ruiz.

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Ruiz, M.G., Solís Casados, D.A., Pliego, J.A. et al. Transformation of Methanol to Hydrocarbons (MTH): Comparison Between MeAPO-36 (Me = Zn, Co, Mg) and Modified ZSM-5 Catalysts. Catal Lett 153, 2493–2503 (2023). https://doi.org/10.1007/s10562-022-04181-2

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