Bio-ethanol valorization towards C4s including 1-butanol over metal modified alumina and zeolite catalysts

Bio-ethanol has been used as a fuel additive in modern society aimed at reducing CO2-emissions and dependence on oil. However, ethanol is unsuitable as fuel supplement in higher proportions due to its physico-chemical properties. One option to counteract the negative effects is to upgrade ethanol in a continuous fixed bed reactor to more valuable C4 products such as 1-butanol providing chemical similarity with traditional gasoline components. Bio-ethanol based valorization products also have other end-uses than just fuel additives. E.g. 1-butanol and ethyl acetate are well characterised industrial solvents and platform chemicals providing greener alternatives. The modern approach is to apply heterogeneous catalysts in the investigated reactions. The research was concentrated on aluminium oxide (Al2O3) and zeolites that were used as catalysts and catalyst supports. The metals supported (Cu, Ni, Co) gave very different product profiles and, thus, a profound view of different catalyst preparation methods and characterisation techniques was necessary. Additionally, acidity and basicity of the catalyst surface have an important role in determining the product profile. It was observed that ordinary determination of acid strength was not enough to explain all the phenomena e.g. the reaction mechanism. One of the main findings of the thesis is based on the catalytically active site which originates from crystallite structure. As a consequence, the overall evaluation of different by-products and intermediates was carried out by combining the information. Further kinetic analysis was carried out on metal (Cu, Ni, Co) supported self-prepared alumina catalysts. The thesis gives information for further catalyst developments aimed to scale-up towards industrially feasible operations

The challenge of efficient synthesis of biofuels from lignocellulose for future renewable transportation fuels

Dehydration of sugars to 5-hydroxymethylfurfural (HMF) has recently been under intensive study by a multitude of research groups. On the other hand, when lignocellulosic biomass is applied as the starting material, very few studies can be found in the open literature. The direct synthesis of HMF, in line with the idea of “one-pot” synthesis strategy from lignocellulose, is demanding since the overall process should encompass dissolution, hydrolysis, and dehydration steps in a single processing unit. Ionic liquid-assisted methods to produce hydroxymethyl-furfural directly from lignocellulosic biomass are reported here together with a short overview of the most important biofuels. In reality, HMF is not suitable to be used as a single-component fuel as such, and, consequently, methods to produce HMF derivatives suitable as liquid fuels are reported.Accepted 6 October 201

One-Pot Liquid-Phase Catalytic Conversion of Ethanol to 1-Butanol over Aluminium Oxide - The Effect of the Active Metal on the Selectivity

Direct catalytic valorization of bioethanol to 1-butanol over different alumina supported catalysts was studied. Thirteen (13) heterogeneous catalysts were screened in search for the optimal material composition for direct one-pot conversion of ethanol to 1-butanol. For the most promising catalyst, a 25% ethanol conversion with 80% selectivity (among liquid carbon products) to 1-butanol could be reached at 250 °C. Additionally, the reaction kinetics and mechanisms were further investigated upon use of the most suitable catalyst candidate

Catalytic Conversion of Ethanol into an Advanced Biofuel: Unprecedented Selectivity for n-Butanol

Taming the beast: Unprecedented selectivity of over 94 % at good (20 %+) conversion was observed for the upgrade of ethanol to the advanced biofuel 1‐butanol with a ruthenium diphosphine catalyst (see picture; P orange, Ru blue). Preliminary mechanistic studies indicate that control over the notoriously uncontrolled acetaldehyde aldol condensation is critical for the high selectivity, and evidence was found for an on‐metal condensation step