Martin Spangsberg Holm

Conversion of Sugars to Lactic Acid Derivatives Using Heterogeneous Zeotype Catalysts

Approaching Lactate Inorganically Conversion of biomass to value-added chemical compounds currently relies in large part on fermentation. For full-scale displacement of petroleum as the chemical industrys primary feedstock, alternative conversion technologies will be necessary. Holm et al. (p. 602) have found that Lewis acidic zeolite derivatives suspended in methanol can catalyze the selective conversion of glucose, fructose, and sucrose sugars to methyl lactate, a versatile synthetic intermediate for commercial products. The catalysts were easily separated from product mixtures and proved robust over six reaction and regeneration cycles. Lewis acid catalysis offers an alternative to fermentation in converting sugars to a commercial chemical feedstock. Presently, very few compounds of commercial interest are directly accessible from carbohydrates by using nonfermentive approaches. We describe here a catalytic process for the direct formation of methyl lactate from common sugars. Lewis acidic zeotypes, such as Sn-Beta, catalyze the conversion of mono- and disaccharides that are dissolved in methanol to methyl lactate at 160°C. With sucrose as the substrate, methyl lactate yield reaches 68%, and the heterogeneous catalyst can be easily recovered by filtration and reused multiple times after calcination without any substantial change in the product selectivity.

Sn-Beta catalysed conversion of hemicellulosic sugars

Conversions of various pentoses and hexoses into methyl lactate has been demonstrated for the Sn-Beta catalyst. It is found that pentoses are converted to methyl lactate in slightly lower yields (∼40%) than what is obtained for hexoses (∼50%), but higher yields of glycolaldehyde dimethyl acetal are observed for the pentoses. This finding is in accordance to a reaction pathway that involves the retro aldol condensation of the sugars to form a triose and glycolaldehyde for the pentoses, and two trioses for hexoses. When reacting glycolaldehyde (formally a C2-sugar) in the presence of Sn-Beta, aldol condensation occurs, leading to the formation of methyl lactate, methyl vinylglycolate and methyl 2-hydroxy-4-methoxybutanoate. In contrast, when converting the sugars in water at low temperatures (100 °C), Sn-Beta catalyses the isomerisation of sugars (ketose–aldose epimers), rather than the formation of lactates.

Tin‐containing Silicates: Alkali Salts Improve Methyl Lactate Yield from Sugars

This study focuses on increasing the selectivity to methyl lactate from sugars using stannosilicates as heterogeneous catalyst. All group I ions are found to have a promoting effect on the resulting methyl lactate yield. Besides, the alkali ions can be added both during the preparation of the catalyst or directly to the solvent mixture to achieve the highest reported yield of methyl lactate (ca. 75 %) from sucrose at 170 °C in methanol. The beneficial effect of adding alkali to the reaction media applies not only to highly defect-free Sn-Beta prepared through the fluoride route, but also to materials prepared by post-treatment of dealuminated commercial Beta zeolites, as well as ordered mesoporous stannosilicates, in this case Sn-MCM-41 and Sn-SBA-15. These findings open the door to the possibility of using other preparation methods or different Sn-containing silicates with equally high methyl lactate yields as Sn-Beta.

Incorporation of tin affects crystallization, morphology, and crystal composition of Sn-Beta

The crystallization of Sn-Beta in fluoride medium is greatly influenced by the amount and type of tin source present in the synthesis gel. By varying the amount of tin in the form of tin(IV) chloride pentahydrate, the time required for crystallization was studied. It was found that tin not only drastically affects the time required for crystallization, but also that the presence of tin changes the morphology of the formed Sn-Beta crystals. For low amounts of tin (Si/Sn = 400) crystallization occurs within four days and the Sn-Beta crystals are capped bipyramidal in shape, whereas for high amounts of tin (Si/Sn = 100) it takes about sixty days to reach full crystallinity and the resulting crystals are highly truncated, almost plate-like in shape. Using SEM-WDS to investigate the tin distribution along transverse sections of the Sn-Beta crystals, a gradient distribution of tin was found in all cases. It was observed that the tin density in the outer parts of the Sn-Beta crystals is roughly twice as high as in the tin depleted core of the crystals. Sn-Beta was found to obtain its maximum catalytic activity for the conversion of dihydroxyacetone to methyl lactate close to the minimum time required for obtaining full crystallinity. At excessive crystallization times, the catalytic activity decreased, presumably due to Ostwald ripening.

High Yield of Liquid Range Olefins Obtained by Converting i-Propanol over Zeolite H-ZSM-5

Methanol, ethanol, and i-propanol were converted under methanol-to-gasoline (MTH)-like conditions (400 degrees C, 1-20 bar) over zeolite H-ZSM-5. For methanol and ethanol, the catalyst lifetimes and conversion capacities are comparable, but when i-propanol is used as the reactant, the catalyst lifetime is increased dramatically. In fact, the total conversion capacity (calculated as the total amount of alcohol converted before deactivation in g(alcohol)/g(zeolite)) is more than 25 times higher for i-propanol compared to the lower alcohols. Furthermore, when i-propanol is used as the reactant, the selectivity toward alkanes and aromatics declines rapidly over time on stream, and at 20 bar of pressure the liquid product mixture consists almost exclusively of C(4)-C(12) alkenes after approximately a third of the full reaction time. This discovery could open a new route to hydrocarbons via i-propanol from syn-gas or biobased feedstocks.

Synthesis and characterization of mesoporous ZSM-5 core-shell particles for improved catalytic properties

Abstract HZSM-5 is a unique catalyst for the conversion of methanol, dimethyl ether and other oxygenates into gasoline. During this process, catalyst deactivation by coking requires frequent regeneration and the improvement of catalyst life time is one of the challenges in catalyst development. In this study, a series of mesoporous samples consisting of a ZSM-5 core and a silicalite shell have been synthesized and characterized by XRD, N2-sorption, IR spectroscopy and electron microscopy techniques. Additionally, desilicated conventional and mesoporous ZSM-5-type samples were investigated. All samples were tested in the MTG reaction, and the results showed that both the shell-coated and the desilicated zeolites are significantly more resistant to coke formation. These results are ascribed to the effect of the removal of structural defects rather than to an improvement of the diffusion properties due to the formation of mesopores.