Hydroxyapatite supported molybdenum oxide catalyst for selective oxidation of methanol to formaldehyde: studies of industrial sized catalyst pellets

The selective oxidation of methanol to formaldehyde is a growing million-dollar industry, and has been commercial for close to a century. The Formox process, which is the largest production process today, utilizes an iron molybdate catalyst, which is highly selective, but has a short lifetime of 6 months due to volatilization of the active molybdenum oxide. Improvements of the process’s lifetime is, thus, desirable. This paper provides an overview of the efforts reported in the scientific literature to find alternative catalysts for the Formox process and critically assess these alternatives for their industrial potential. The catalysts can be grouped into three main categories: Mo containing, V containing, and those not containing Mo or V. Furthermore, selected interesting catalysts were synthesized, tested for their performance in the title reaction, and the results critically compared with previously published results. Lastly, an outlook on the progress for finding new catalytic materials is provided as well as suggestions for the future focus of Formox catalyst research.

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Selective Oxidation of Methanol on Iron-Chromium-Molybdenum Oxide Catalysts

New Developments in Selective Oxidation II, Proceedings of the Second World Congress and Fourth European Workshop Meeting - Studies in Surface Science and Catalysis ◽

10.1016/s0167-2991(08)63475-8 ◽

1994 ◽

pp. 787-794 ◽

Cited By ~ 1

Author(s):

D. Klissurski ◽

V. Rives ◽

Y. Pesheva ◽

I. Mitov ◽

R. Stoyanova

Keyword(s):

Selective Oxidation ◽

Molybdenum Oxide ◽

Oxide Catalysts ◽

Oxidation Of Methanol ◽

Iron Chromium

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Modeling of the molybdenum loss in iron molybdate catalyst pellets for selective oxidation of methanol to formaldehyde

Chemical Engineering Journal ◽

10.1016/j.cej.2018.12.142 ◽

2019 ◽

Vol 361 ◽

pp. 1285-1295 ◽

Cited By ~ 5

Author(s):

Kristian Viegaard Raun ◽

Jeppe Johannessen ◽

Kaylee McCormack ◽

Charlotte Clausen Appel ◽

Sina Baier ◽

...

Keyword(s):

Selective Oxidation ◽

Iron Molybdate ◽

Oxidation Of Methanol ◽

Catalyst Pellets

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Highly Stable Apatite Supported Molybdenum Oxide Catalysts for Selective Oxidation of Methanol to Formaldehyde: Structure, Activity and Stability

ChemCatChem ◽

10.1002/cctc.202101220 ◽

2021 ◽

Author(s):

Joachim Thrane ◽

Christopher Falholt Elvebakken ◽

Mikkel Juelsholt ◽

Troels Lindahl Christiansen ◽

Kirsten M. Ø. Jensen ◽

...

Keyword(s):

Selective Oxidation ◽

Molybdenum Oxide ◽

Oxide Catalysts ◽

Oxidation Of Methanol ◽

Structure Activity

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Kinetics of oxidation of methanol with air on a chromium-molybdenum oxide catalyst supported on porous α-Al2O3

Reaction Kinetics and Catalysis Letters ◽

10.1007/bf02342571 ◽

1976 ◽

Vol 4 (3) ◽

pp. 307-313 ◽

Cited By ~ 3

Author(s):

K. Ts. Cheshkova ◽

V. N. Bibin ◽

B. I. Popov

Keyword(s):

Molybdenum Oxide ◽

Oxide Catalyst ◽

Kinetics Of Oxidation ◽

Oxidation Of Methanol ◽

Α Al2o3 ◽

Kinetics Of

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

Catalysts ◽

10.3390/catal10010082 ◽

2020 ◽

Vol 10 (1) ◽

pp. 82 ◽

Cited By ~ 4

Author(s):

Joachim Thrane ◽

Lars Fahl Lundegaard ◽

Pablo Beato ◽

Uffe Vie Mentzel ◽

Max Thorhauge ◽

...

Keyword(s):

Selective Oxidation ◽

Molybdenum Oxide ◽

Sol Gel ◽

Earth Metal ◽

Operating Conditions ◽

Packed Bed Reactor ◽

Stoichiometric Ratio ◽

Alkali Earth Metal ◽

Alkali Earth ◽

Oxidation Of Methanol

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.

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