EnabledCatalysts Patent Spotlight

BR112019007821B1 : Method For Isomerization of a Feedstock Dehydration Non Linear Primary Alcohol in the Presence of Injection of Water and a Catalyst Comprising an Iron Type Crutcher MFS Or [FR3058415A1]

Michelle

BR112019007821B1 : Method For Isomerization of a Feedstock Dehydration Non Linear Primary Alcohol in the Presence of Injection of Water and a Catalyst Comprising an Iron Type Crutcher MFS Or [FR3058415A1]

Applicants: FRENCH INSTITUTE OF PETROLEUM SA , TOTALENERGIES SE

1st Inventor: Sylyie Maury

This month’s catalyst patent is a granted publication in Brazil to the French Institute of Petroleum (IFPEN) and Total Energies SE. The work relates to production of olefins by alcohol dehydration over a zeolite catalyst. The first inventor on the patent is Dr Sylvie Maury from IFPEN, France. The patent comes from a French priority FR20160060803 published 08-Nov-2016. There are also French and US granted family members.
The patent more specifically relates to the dehydration of iso-butanol to C4 olefins. The catalyst is prepared from a mixture of commercial NH4-ferrierite and silica binder(s) which are kneaded in an aqueous solution of triethylammonium TEAOH. The mixture is then extruded, dried, and calcined to give extrudates of 2-4 mm. Ferrierite is chosen because it has at least one channel with a ring of 8 oxygen atoms (8MR).

Catalyst testing is carried out in either a single or dual reactor with fixed beds operating in “down flow” mode. Water/iso-butanol feed is vapourised and passed over the catalyst bed at 8 bar/300-400°C. With 7% water added into the iso-butanol feed, the best results achieved were 97.8% olefin selectivity with a ratio of n-butenes/all butenes of 84.1% after 72 h at a conversion of 99%. The main by-product was iso-butyraldehyde. Further experiments were carried out with 30% water in the feed. When no water was added to the iso-butanol feed, a rapid deactivation of the catalyst was observed as shown in Figure 1 below.

Figure 1. Activity Testing of Ferrierite Catalysts for Iso-Butanol Conversion to C4-Olefins
Example 2: 30% water; Example 3: 0% water

Homogeneous Catalysis using Cycloruthenated Complexes

Michelle

Homogeneous Catalysis using Cycloruthenated Complexes

A recent review from the University of Manchester highlights the potential and versatility of cycloruthenated complexes for a variety of homogeneous reactions including C–H activation, Z-selective olefin metathesis, asymmetric cyclopropanations, cycloadditions, transfer hydrogenation, and chiral-at-metal catalysis. Research on late-stage functionalisation of complex molecules such as active pharmaceutical ingredients (APIs) including diazepam, atazanavir and sulfaphenazole was highlighted (Findlay, Domingo-Legarda, McArthur, Yen, & Larrosa, 2022)

Figure 1. Use of Cycloruthenated Complexes for Late Stage Functionalisation of Molecules (Findlay, Domingo-Legarda, McArthur, Yen, & Larrosa, 2022)



Research in this area has been ongoing for decades, however it is interesting when patents start to appear which can indicate future potential for commercialisation. One such patent was recently applied for by a French consortium in collaboration with the University of California describing a new class of homogeneous ruthenium catalysts for asymmetric ring-opening cross-metathesis (AROCM) reactions. The patent application describes (R)- and (S)-CAAC-Ru metathesis catalysts (CAAC = Cyclic Alkyl Amino Carbene) which have chiral cyclic (alkyl)(amino) carbene ligands. An example for an AROCM reaction is shown in Figure 2 below. (Jazzar, et al., 2022)

Enabled Future Limited has recently completed a major consulting assignment for a multinational company (MNC) on the use of PGM homogeneous catalysts for a range of fine chemicals including estimates of catalyst and metal demand based on scientific and commercial market information.


Figure 2 Asymmetric Ring Opening Cross Metathesis (AROCM) using a novel ruthenium- carbene complex. (Jazzar, et al., 2022)

Findlay, M. T., Domingo-Legarda, P., McArthur, G., Yen, A., & Larrosa, I. (2022). Catalysis with cycloruthenated complexes. Chem. Sci, 13, 3335-3362.
Jazzar, R., Betrand, G., Vermersch, F., Vanthuyne, N., Mauduit, M., & Morvan, J. (2022, January 13). WO2022008679A1. RUTHENIUM COMPLEXES, THEIR OPTICALLY PURE ENANTIOMERS AND USES THEREOF.

BASF Formaldpure™ Catalyst receives 2022 Edison Patent Award

BASF Formaldpure™ Catalyst receives 2022 Edison Patent Award

Michelle

BASF Formaldpure™ Catalyst receives 2022 Edison Patent Award

BASF reported this week (Nov 3) that the prestigious Thomas Alva Edison Patent Award 2022 has been awarded to its researchers in the USA, Germany, and China for their work on the Formaldpure™ Catalyst which converts formaldehyde into carbon dioxide and water. The technology is employed for removing indoor pollutants at room temperature.

The award was made by the Research and Development Council of New Jersey and presented at a ceremony held on November 3, 2022, to David Weinberger, Wolfgang Ruettinger, Pascaline Tran, Laif Alden, Ting Gu, Anju Shi, Nils Lawrenz and Lukas Wengeler who work at BASF’s sites in Iselin, New Jersey, and Ludwigshafen, Germany, as well as Shanghai, China.

Indoor formaldehyde levels which arise from degassing of furniture, coatings, insulation, and other household items is a source of concern for human health. The Formaldpure™ technology consists of a catalyst supported on a thin and flexible foam substrate which can easily be fitted into indoor air purifiers by customers in commercial and residential settings. It works at temperatures up to 90˚C, 0-90% humidity and 6-50 Pa. The structure of the catalyst and typical performance is shown in Figure.1 below1.

Figure 1. BASF Formaldpure-F Formaldehyde Abatement Catalyst and Performance1 (Performance subject to different settings)

Patents assigned to BASF which appear to relate to this technology include a granted US patent which discloses a catalyst preparation route in Example 1 as follows:

“73.4 g of Ceria and 73.4 g of Cryptomelane (potassium manganese oxide) are dispersed in 191 g of water, and a solution of 4.8 g alumina sol (Dispal P3) and 4.8 g acetic acid in 16.8 g water is added to the resulting slurry. A solution of cellulose base thickener (0.2 g) is added to the slurry with vigorous mixing. This slurry is used to coat ceramic monolithic substrates (cordierite; 400 cells per square inch). Afterwards the coated monolith is dried at 120° C. for 2 h and calcined at 250° C. for 1 h. The coating is repeated until the weight gain of the monolithic substrate is 2 g/in3”.2

This preparation route gave a catalyst which maintained over 80% formaldehyde conversion efficiency for up to 4.5 g of cumulative formaldehyde and reduced the formaldehyde concentrations down from about 1100 ppb to 200 ppb, a clean air delivery rate (CADR) 2-3 times better than comparative examples in the patent.

  1. BASF. (2022, June 9). Formaldpure F Produt Sheet. Retrieved from BASF: file:///C:/Users/Michelle/Desktop/EFL%20New/EFL%20Patent%20Spotlights/BASF_10701_Formaldpure_Datasheet_A4_Rev.06_2022.pdf
  2. Ruettinger, W., Laif, A., Pascaline, R., Weinberger, D., Anju, S., & Feng, Z. (2022, January 11). US11219882B2. Catalyst device for treatment of formaldehyde and volatile organic compounds.