Alkali Earth Metal Molybdates as Catalysts for the Selective Oxidation of Methanol to Formaldehyde — Selectivity, Activity, and Stability

Joachim Thrane*, Lars Fahl Lundegaard, Pablo Beato, Uffe Vie Mentzel, Max Thorhauge, Anker Degn Jensen, Martin Høj

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

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Abstract

Alkali earth metal molybdates (MMoO4, M = Mg, Ca, Sr, and Ba) were investigated as catalysts for the selective oxidation of methanol to formaldehyde in the search for more stable alternatives to the current industrial iron molybdate catalyst. The catalysts were prepared by either sol-gel synthesis or co-precipitation with both stoichiometric ratio (Mo:M = 1.0) and 10 mol% to 20 mol% excess Mo (Mo:M = 1.1 to 1.2). The catalysts were characterized by X-ray diffraction (XRD), nitrogen physisorption, Raman spectroscopy, temperature programmed desorption of CO2 (CO2-TPD), and inductively coupled plasma (ICP). The catalytic performance of the catalysts was measured in a lab-scale, packed bed reactor setup by continuous operation for up to 100 h on stream at 400 °C. Initial selectivities towards formaldehyde of above 97% were achieved for all samples with excess molybdenum oxide at MeOH conversions between 5% and 75%. Dimethyl ether (DME) and dimethoxymethane (DMM) were the main byproducts, but CO (0.1%–2.1%) and CO2 (0.1%–0.4%) were also detected. It was found that excess molybdenum oxide evaporated from all the catalysts under operating conditions within 10 to 100 h on stream. No molybdenum evaporation past the point of stoichiometry was detected.
Original languageEnglish
Article number82
JournalCatalysts
Volume10
Issue number1
Number of pages16
ISSN2073-4344
DOIs
Publication statusPublished - 2020

Keywords

  • Formox process
  • Selective oxidation
  • Formaldehyde
  • Molybdate
  • Methanol
  • Heterogeneous catalysis

Cite this

@article{bdfefddead4949f2abd81f5c3f21bbcb,
title = "Alkali Earth Metal Molybdates as Catalysts for the Selective Oxidation of Methanol to Formaldehyde — Selectivity, Activity, and Stability",
abstract = "Alkali earth metal molybdates (MMoO4, M = Mg, Ca, Sr, and Ba) were investigated as catalysts for the selective oxidation of methanol to formaldehyde in the search for more stable alternatives to the current industrial iron molybdate catalyst. The catalysts were prepared by either sol-gel synthesis or co-precipitation with both stoichiometric ratio (Mo:M = 1.0) and 10 mol{\%} to 20 mol{\%} excess Mo (Mo:M = 1.1 to 1.2). The catalysts were characterized by X-ray diffraction (XRD), nitrogen physisorption, Raman spectroscopy, temperature programmed desorption of CO2 (CO2-TPD), and inductively coupled plasma (ICP). The catalytic performance of the catalysts was measured in a lab-scale, packed bed reactor setup by continuous operation for up to 100 h on stream at 400 °C. Initial selectivities towards formaldehyde of above 97{\%} were achieved for all samples with excess molybdenum oxide at MeOH conversions between 5{\%} and 75{\%}. Dimethyl ether (DME) and dimethoxymethane (DMM) were the main byproducts, but CO (0.1{\%}–2.1{\%}) and CO2 (0.1{\%}–0.4{\%}) were also detected. It was found that excess molybdenum oxide evaporated from all the catalysts under operating conditions within 10 to 100 h on stream. No molybdenum evaporation past the point of stoichiometry was detected.",
keywords = "Formox process, Selective oxidation, Formaldehyde, Molybdate, Methanol, Heterogeneous catalysis",
author = "Joachim Thrane and Lundegaard, {Lars Fahl} and Pablo Beato and Mentzel, {Uffe Vie} and Max Thorhauge and Jensen, {Anker Degn} and Martin H{\o}j",
year = "2020",
doi = "10.3390/catal10010082",
language = "English",
volume = "10",
journal = "Catalysts",
issn = "2073-4344",
publisher = "M D P I AG",
number = "1",

}

Alkali Earth Metal Molybdates as Catalysts for the Selective Oxidation of Methanol to Formaldehyde — Selectivity, Activity, and Stability. / Thrane, Joachim; Lundegaard, Lars Fahl; Beato, Pablo; Mentzel, Uffe Vie; Thorhauge, Max; Jensen, Anker Degn; Høj, Martin.

In: Catalysts, Vol. 10, No. 1, 82, 2020.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Alkali Earth Metal Molybdates as Catalysts for the Selective Oxidation of Methanol to Formaldehyde — Selectivity, Activity, and Stability

AU - Thrane, Joachim

AU - Lundegaard, Lars Fahl

AU - Beato, Pablo

AU - Mentzel, Uffe Vie

AU - Thorhauge, Max

AU - Jensen, Anker Degn

AU - Høj, Martin

PY - 2020

Y1 - 2020

N2 - Alkali earth metal molybdates (MMoO4, M = Mg, Ca, Sr, and Ba) were investigated as catalysts for the selective oxidation of methanol to formaldehyde in the search for more stable alternatives to the current industrial iron molybdate catalyst. The catalysts were prepared by either sol-gel synthesis or co-precipitation with both stoichiometric ratio (Mo:M = 1.0) and 10 mol% to 20 mol% excess Mo (Mo:M = 1.1 to 1.2). The catalysts were characterized by X-ray diffraction (XRD), nitrogen physisorption, Raman spectroscopy, temperature programmed desorption of CO2 (CO2-TPD), and inductively coupled plasma (ICP). The catalytic performance of the catalysts was measured in a lab-scale, packed bed reactor setup by continuous operation for up to 100 h on stream at 400 °C. Initial selectivities towards formaldehyde of above 97% were achieved for all samples with excess molybdenum oxide at MeOH conversions between 5% and 75%. Dimethyl ether (DME) and dimethoxymethane (DMM) were the main byproducts, but CO (0.1%–2.1%) and CO2 (0.1%–0.4%) were also detected. It was found that excess molybdenum oxide evaporated from all the catalysts under operating conditions within 10 to 100 h on stream. No molybdenum evaporation past the point of stoichiometry was detected.

AB - Alkali earth metal molybdates (MMoO4, M = Mg, Ca, Sr, and Ba) were investigated as catalysts for the selective oxidation of methanol to formaldehyde in the search for more stable alternatives to the current industrial iron molybdate catalyst. The catalysts were prepared by either sol-gel synthesis or co-precipitation with both stoichiometric ratio (Mo:M = 1.0) and 10 mol% to 20 mol% excess Mo (Mo:M = 1.1 to 1.2). The catalysts were characterized by X-ray diffraction (XRD), nitrogen physisorption, Raman spectroscopy, temperature programmed desorption of CO2 (CO2-TPD), and inductively coupled plasma (ICP). The catalytic performance of the catalysts was measured in a lab-scale, packed bed reactor setup by continuous operation for up to 100 h on stream at 400 °C. Initial selectivities towards formaldehyde of above 97% were achieved for all samples with excess molybdenum oxide at MeOH conversions between 5% and 75%. Dimethyl ether (DME) and dimethoxymethane (DMM) were the main byproducts, but CO (0.1%–2.1%) and CO2 (0.1%–0.4%) were also detected. It was found that excess molybdenum oxide evaporated from all the catalysts under operating conditions within 10 to 100 h on stream. No molybdenum evaporation past the point of stoichiometry was detected.

KW - Formox process

KW - Selective oxidation

KW - Formaldehyde

KW - Molybdate

KW - Methanol

KW - Heterogeneous catalysis

U2 - 10.3390/catal10010082

DO - 10.3390/catal10010082

M3 - Journal article

VL - 10

JO - Catalysts

JF - Catalysts

SN - 2073-4344

IS - 1

M1 - 82

ER -