Conversion of glycerol to the valuable intermediates acrolein and allyl alcohol in the presence of heterogeneous catalysts

Ülgen, Arda; Hölderich, Wolfgang F.

doi:3078

Conversion of glycerol to the valuable intermediates acrolein and allyl alcohol in the presence of heterogeneous catalysts = Heterogenkatalysierte Umsetzung von Glycerin zu Acrolein und Allylalkohol

Ülgen, Arda (Author)

2010

Verantwortlichkeitsangabevorgelegt von Arda Ülgen

ImpressumAachen : Publikationsserver der RWTH Aachen University 2010

UmfangIII, 137 S. : graph. Darst.

Aachen, Techn. Hochsch., Diss., 2009

Genehmigende Fakultät
Fak01

Hauptberichter/Gutachter
Hölderich, Wolfgang F. (Thesis advisor)

Tag der mündlichen Prüfung/Habilitation
2009-09-14

Online
URN: urn:nbn:de:hbz:82-opus-30784
URL: https://publications.rwth-aachen.de/record/63757/files/3078.pdf

Einrichtungen

Inhaltliche Beschreibung (Schlagwörter)
Grüne Chemie (Genormte SW) ; Acrolein (Genormte SW) ; Allylalkohol (Genormte SW) ; Glycerin (Genormte SW) ; Heterogene Katalyse (Genormte SW) ; Chemie (frei) ; green chemistry (frei) ; gylcerol (frei) ; allyl alcohol (frei) ; heterogeneous catalysis (frei)

Thematische Einordnung (Klassifikation)
DDC: 540
rvk: VN 7347 * VE 7047

Kurzfassung
Thema der vorliegenden Arbeit ist die Umsetzung von Glycerin zu Acrolein / Allylalkohol. Sowohl Acrolein als auch Allylalkohol werden großtechnisch aus Propylen bzw. Erdöl hergestellt. Glycerin, auf der anderen Seite, ist ein kostengünstiges Edukt, das bei der Herstellung von Biodiesel abfällt. Die heterogenkatalysierte Gasphasenumsetzung von Glycerin zu Acrolein in der Anwesenheit von WO3/TiO2 bzw. WO3/ZrO2 stellt den Kern der Arbeit dar. Die Darstellung von Allylalkohol sowie einige mechanistische Studien wurden ebenfalls im Rahmen der vorliegenden Arbeit vorgestellt.

The attractiveness of crude oil as a feed stock for the chemical industry decreases with its scarcity and its correlated increasing price. Simultaneously, environmental issues as global warming underlines the necessity of alternative feed stocks and benign processes. The production of diesel fuel from plant oils is considered as a solution to these problems. However, the transesterification process for bio-diesel production leads to larger amounts of glycerol as a by product. The overproduced bio-diesel glycerol did not only suppress its price to very low levels but also loaded extra costs on the bio-diesel producers in terms of storage. Therefore there is great interest to use glycerol as starting material for its transformation in highly valuable intermediates for the chemical industry. Acrolein is an important intermediate in the organic industrial chemistry. Refined acrolein is used especially for the production of methionin. Much larger quantities are needed for the production of acrylic acid which is the monomer of poly acrylic acid. Poly acrylic acid is used as super absorbent mainly in diapers and hygienic pads. Currently acrolein is produced from propylene, which is originated from crude oil. Allyl alcohol is another intermediate with increasing application areas. It is used for the production of epichlorohydrine and 1-4 butane diol. Allyl alcohol is also currently produced from crude oil based materials. The subject of the present work is the heterogeneously catalyzed continious conversion of glycerol to the mentioned valuable intermediates; acrolein and ally alcohol. Shifting the source of carbon for the production of these chemicals from propylene to glycerol would not only encourage bio-diesel producers by enabling commercial possibilities for their by-product, but it would also avoid using crude oil in the production of acrolein and allyl alcohol. By that, acrolein, allyl alcohol and mentioned sequent chemicals would be biomass based and a CO2-neutral production would be provided. The development of suitable catalysts, screening of these catalysts under different experimental conditions, as well as investigation of the reaction routes, the side products and relationships between the properties of the catalyst and their performance in particular on the acrolein formation represent the scope of this work. The following achievements represent the core and the key findings of the present work. The surface acidity/basicity of the catalyst was found to be crucial for its performance in terms of acrolein yield. These catalyst properties could be manipulated by several measures. The catalyst system, WO3/TiO2, was revealed to be very suitable for the dehydration of glycerol to acrolein, outperforming the known catalysts in the literature up to date. The direct conversion of glycerol to allyl alcohol was discovered. The direct production of allyl alcohol from glycerol represents a novel and benign process.

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