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Doctoral thesis . 2013
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Prozessentwicklung zur biotechnologischen Produktion von Acrolein aus Nebenprodukten der Bioethanolherstellung

Process development for the biotechnological production of acrolein from bioethanol production by-products
Authors: Oehmke, Sebastian;

Prozessentwicklung zur biotechnologischen Produktion von Acrolein aus Nebenprodukten der Bioethanolherstellung

Abstract

Da fossile Quellen endlich sind, werden Chemikalien aus nachwachsenden Rohstoffen immer interessanter für die Forschung und Industrie. Zu den vielversprechenden Plattformchemikalien gehört das Stoffpaar 3-Hydroxypropionaldehyd/ Acrolein. Jedoch sind bisherige Ansätze für eine wirtschaftliche Produktion von 3-Hydroxypropionaldehyd/ Acrolein im industriellen Maßstab nicht ausreichend. Deshalb wurde in dieser Arbeit geprüft, inwieweit sich Schlempe, ein glycerinhaltiges Nebenprodukt der Bioethanolherstellung, zur 3-Hydroxypropionaldehyd/ Acrolein Produktion nutzen lässt und inwieweit diese Produktion in den Bioethanolprozess im Sinne des Bioraffineriekonzeptes integriert werden kann, um bestehende Probleme zu lösen und Produktionskosten zu reduzieren. Dazu wurden ansatzweise und kontinuierliche Versuche im 5 ml bis 2 l Maßstab sowie Berechnungen in den Bereichen Biokatalysatorproduktion, Biotransformation, Aufreinigung und Kostenschätzung durchgeführt. Der Ganzzellbiokatalysator Lactobacillus reuteri ATCC 53608 ist nicht in der Lage die Hefezellen aus Bioethanolproduktionsrückständen für sein Wachstum zu nutzen, jedoch hat sich gezeigt, dass er nicht alle Nährstoffe im MRS Medium benötigt und Hefeextrakt als einzigste Quelle von Aminosäuren und Vitaminen für sein Wachstum und seine Enzymproduktion ausreichend ist. Die 3-HPA Produktion ist in Bioethanolproduktionsrückständen 68 % höher als in einer vergleichbaren Glycerinlösung bei gleichen Bedingungen und es wird weniger Biokatalysator benötigt. Eine Kombination aus Dehydratisierung und einfacher Destillation ist geeignet, um das 3-Hydroxypropionaldehyd simultan in Acrolein umzuwandeln und aus der Biotransformationsbrühe bei 37°C abzutrennen, wodurch 105 ± 8 g/l Acrolein in Wasser mit hoher Reinheit gewonnen werden können. Die Kostenschätzung eines möglichen Prozesses hat gezeigt, dass die ermittelten Kosten des Acroleins in einer Größenordnung liegen, welche zeigt, dass der angedachte Prozess bei entsprechender Optimierung in naher Zukunft zu den Produktionskosten aus Rohölderivaten aufschließen kann. Zusammenfassend konnte gezeigt werden, dass sich eine Anlehnung an den Bioethanolprozess nutzen lässt, um die biotechnologische Produktion von 3-Hydroxypropionaldehyd/ Acrolein aus nachwachsenden Rohstoffen zu verbessern.

Since fossile rescources are of limited availability, chemicals from renewable resources become more interesting for scientists and the industry. Promising platform chemicals include 3-hydroxypropionaldehyde and its anhydride acrolein. However, existing approaches are not sufficient for an economic production in industrial scale. Therefore, it was examined in this thesis how far stillage, a glycerol containing byproduct of the bioethanol production process, can be used for the 3-hydroxypropionaldehyde/ acrolein production and how far this production can be integrated into the bioethanol process according to the biorefinery concept to solve existing problems and to reduce production costs. Calculations as well as batchwise and continuous experiments were carried out in 5 ml to 2 l scale in the area of biocatalyst production, biotransformation, purification and cost estimation. The whole cell biocatalyst Lactobacillus reuteri ATCC 53608 is not able to use the yeast cells from bioethanol production residues for its growth. However, it has been shown that it does not need all the nutrients in MRS medium and yeast extract is sufficient as the only source of amino acids and vitamins for its growth and enzyme production. The 3-HPA production in bioethanol production residues is 68 % higher than in a comparable aqueous glycerol solution under the same conditions and it requires less biocatalyst. A combination of dehydration and simple distillation is suitable to convert 3-hydroxypropionaldehyde into acrolein and separate it from the biotransformation broth at 37 ° C. 105 ± 8 g/l acrolein in aqueous solution were obtained in high purity. The cost estimation of a possible process has shown that the calculated cost for acrolein can likely catch up with production costs from crude oil in the near future with appropriate optimization. Hence it was shown that basing the process on stillage from the bioethanol process can improve the biotechnological production of 3-hydroxypropionaldehyde/ acrolein from renewable resources.

Country
Germany
Keywords

biorefinery, Chemiekalie, Engineering and allied operations, 58.30:Biotechnologie, Bioethanol, 58.30, platform chemical, 620, Bioraffinerie, Plattformchemikalie, 3-Hydroxypropionaldehyd, 3-Hydroxypropionaldehyde, biotransformation, Acrolein, Biotransformation, bioethanol

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popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
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