Catalysis and petrochemistry
Theoretical and scientific-technical collection
ISSN 2707-5796 (Online), ISSN 2412-4176 (Print)
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Kataliz ta naftohimia: 2020, Vol.30, 43-47.

https://doi.org/10.15407/kataliz2020.30.043

Conversion of fructose into methyl lactate over SnO2/Al2O3 catalystin flow regime

S.V. Prudius, N.L. Hes, A.M. Mylin, V.V. Brei

Institute for Sorption and Problems of Endoecology of National Academy of Sciences of Ukraine
13 General Naumov Str., Kyiv 03164, Ukraine
E-mail: svitprud@gmail.com

ABSTRACT

In recent years, numerous researchers have focused on the development of catalytic methods for processing of biomass-derived sugars into alkyl lactates, which are widely used as non-toxic solvents and are the starting material for obtaining monomeric lactide. In this work, the transformation of fructose into methyl lactate on Sn-containing catalyst in the flow reactor that may be of practical interest was studied. The supported Sn-containing catalyst was obtained by a simple impregnation method of granular γ-Al2O3. The catalytic experiments were performed in a flow reactor at temperatures of 160-190 °C and pressure of 3.0 MPa. The 1.6-9.5 wt. % fructose solutions in 80 % aqueous methanol were used as a reaction mixture. It was found that addition to a reaction mixture of 0.03 wt. % potassium carbonate leads to the increase in selectivity towards methyl lactate on 15 % at 100 % conversion of fructose. Products of the target reaction С6Н12О6 + 2СН3ОН = 2С4Н8О3 + 2Н2О were analyzed using 13C NMR method. The following process conditions for obtaining of 65 mol % methyl lactate yield at 100 % fructose conversion were found: use of 4.8 wt. % fructose solution in 80 % methanol, 180 °С, 3.0 МПа and a load on catalyst 1.5 mmol C6H12O6/mlcat/h at contact time of 11 minutes. The catalyst productivity is 2.0 mmol C4H8O3/mlcat/h and the by-products are  1,3-dihydroxyacetone dimethyl acetal (20 %) and 5-hydroxymethylfurfural (10 %). It should be noted that a racemic mixture of L- and D-methyl lactates has been obtained by conversion of D-fructose on the SnO2/Al2O3 catalyst. The SnO2/Al2O3 catalyst was found to be stable for 6 h while maintaining full fructose conversion at 55–70 % methyl lactate selectivity. After regeneration the catalyst completely restores the initial activity. 

KEYWORDS

methyl lactate, fructose conversion, tin-containing catalyst

REFERENCES

1. Pereira C.S.M., Silva V.M.T.M., Rodrigues A.E. Ethyllactate as a solvent: Properties, applications and production processes - a review. Green Chemistry. 2011. 13. 2658-2671. [in English]
https://doi.org/10.1039/c1gc15523g

2. Patent 7652167 B2. US. 10/894,307. Miller D.J., Asthana N., Kolah A., Lira C.T. Process for production of organic esters. USA. 26.01.2010. [in English]

3. Patent 2011/0160480 A1. US. 13/056,292. Hottois D., Bruneau A., Bogaert J.-Ch., Coszach Ph. Continuous process for obtaining a lactic esters. Belgium. 30.07.2011. [in English]

4. Patent 8592609 B2. US. 12/809,216. Coszach Ph., Mariage P.-A. Method for obtaining lactide. Belgium. 26.11.2013. [in English]

5. Patent 141885 Ukraine. С07С69/75. Brei V.V., Shchutskyi I.V., Varvarin A.M., Levytska S.I. Sposib oderzhannia laktidu iz alkillaktativ. Ukraine. 27.04.2020. [in Ukrainian]

6. Zhang H., Hu Yu., Qi L., He J., Li H., Yang S. Chemocatalytic Production of Lactates from Biomass-Derived Sugars. International Journal of Chemical Engineering. 2018. Article ID 7617685. 18. [in English]
https://doi.org/10.1155/2018/7617685

7. Holm M.S., Saravanamurugan S., Taarning, E. Conversion of sugars to lactic acid derivatives using heterogeneous zeotype catalysts. Science. 2010. 328. 602-605. [in English]
https://doi.org/10.1126/science.1183990

8. Tolborg S., Sadaba I., Osmundsen C.M., Fristrup P., Holm M.S., Taarning E. Tin-containing silicates: alkali salts improve methyl lactate yield from sugars. ChemSusChem. 2015. 8 (4). 613-617. [in English]
https://doi.org/10.1002/cssc.201403057

9. Zhang J., Wang L., Wang G., Chen F., Zhu J., Wang Ch., Bian Ch., Pan Sh., Xiao F.-Sh. Hierarchical Sn-Beta zeolite catalyst for the conversion of sugars to alkyl lactates. ACS Sustainable Chemistry and Engineering. 2017. 5 (4). 3123-3131. [in English]
https://doi.org/10.1021/acssuschemeng.6b02881

10. Yang L., Yang X., Tian E., Vattipalli V., Fan W., Lin H. Mechanistic insights into the production of methyl lactate by catalytic conversion of carbohydrates on mesoporous Zr-SBA-15. Journal of Catalysis. 2016. 333. 207-216. [in English]
https://doi.org/10.1016/j.jcat.2015.10.013

11 Prudius S.V., Hes N.L., Brei V.V. Conversion of D-fructose into ethyl lactate over a supported SnO2-ZnO/Al2O3 catalyst. Colloids Interfaces. 2019. 3 (16). 1-8. [in English]
https://doi.org/10.3390/colloids3010016

12. Patent 2 184 270 B1. EP. 09013782.9. Taarning E., Saravanamurugan S., Holm М.S. Zeolite-catalyzed preparation of alpha-hydroxy carboxylic acid compounds and esters thereof. Denmark. 13.02.2013. Bulletin 2013/07. [in English]

13. Padovan D., Tolborg S., Botti L., Taarning E., Sadaba I., Hammond C. Overcoming catalyst deactivation during the continuous conversion of sugars to chemicals: maximizing the performance of Sn-Beta with a little drop of water. Reaction Chemistry & Engineering. 2018. 3. 155-163. [in English]
https://doi.org/10.1039/C7RE00180K

14. Hoang T.M.C., van Eck E.R.H., Bula W.P., Gardeniers J.G.E., Lefferts L., Seshan K. Humin based by-products from biomass processing as a potential carbonaceous source for synthesis gas production. Green Chem. 2015. 17. 959. [in English]
https://doi.org/10.1039/C4GC01324G

15. Sharanda M.E., Levytska S.I., Prudius S.V., Mylin A.M., Brei V.V. Study of glucose hydrogenolysis over Cu-oxides. Him. Fiz. Tehnol. Poverhni. 2018. 9 (2). 134. [in English]
https://doi.org/10.15407/hftp09.02.134

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