CATALYTIC SYNTHESIS OF GLYCOLIC ACID AND ITS METHYL ESTER FROM GLYOXAL
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Keywords

glycolic acid, methyl glycolate, glyoxal, oxide catalysts

How to Cite

Levytska, S., & Mylin, A. (2021). CATALYTIC SYNTHESIS OF GLYCOLIC ACID AND ITS METHYL ESTER FROM GLYOXAL. Ukrainian Chemistry Journal, 86(12), 134-145. https://doi.org/10.33609/2708-129X.86.12.2020.134-145

Abstract

Glycolic acid is practically non-toxic to humans, has bactericidal properties and a weak odor, which makes it widely used in food (as a flavoring and preservative) textile (as a dye and tanning agent), cosmetics and pharmaceuticals (as a keratolytic and a skin care agen). Glycolic acid can also be converted to biodegradable polymer with good mechanical properties and excellent biocompatibility, wich is used for different medical applications. In industry, glycolic acid is obtained by carbonylation of formaldehyde using as catalysts quite aggressive acids (H2SO4, HCl, HF), hydrolysis of hydroxyacetonitrile under the influence of acids (H2SO3, H3PO3) or the enzyme nitrilase and saponification of chloroacetic acid with a double excess of alkali (NaOH, KOH). In addition to the non-ecological nature of used raw materials for this process there is a problem associated of purification of the product especially from homogeneous catalysts. The process of obtaining glycolic acid and its methyl ester from glyoxal over a number of solid acid and basic catalysts based on mixed oxides of aluminum, tin, titanium, zirconium, and magnesium has been studied. In study, commercially available 40% aqueous solution of glyoxal, anhydrous glyoxal trimer (Sigma-Aldrich, 95%) and methanol (99%, Merck) were used. Catalytic experiments were carried out in rotated steel autoclave (60 rpm) for 0.5–5 hours at temperatures of 100–170 °C. It is shown that the synthesized oxide catalysts after 5 h of reaction at 100 °C provide up to 98% conversion of an aqueous solution of glyoxal to glycolic acid with a selectivity of 83–100%.It was found that over the studied basic catalysts the undesirable oligomerization process of the formed glycolic acid occurred to a lesser extent and as a result the yield of monoglycolic acid was much higher (60–69%) than over acid catalysts (28–40%). The most selective MgO-ZrO2 catalyst after 1 h of the reaction at 150 °C of methanolicglyoxal solution provides almost 100% yield of methyl glycolate.

https://doi.org/10.33609/2708-129X.86.12.2020.134-145
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References

Miltenberger K. Hydroxycarboxylic acid, Aliphatic. Ullman’s encyclopedia of industrial chemistry. 2012. 18: 481. Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimDOI: 10.1002/14356007.a13_507

Kiyoura T., Kogure Y.Synthesis of hydroxyacetic acid and its ether from glyoxalcatalyzed by multivalent metal ions. Applied Catalysis A. 1997. 156: 97.

Ohshima T., Yamamoto Y., Takaki U., Inoue Y., Saeki T., Itou K. Maegawa Y., Iwasakia T., Mashima K. Theoretical study of Al(III)-catalyzed conversion of glyoxal to glycolic acid: dual activated 1,2-hydride shift mechanism by protonated Al(OH)3 species. Chemical Communication. 2009. 2688.

Salusjärvi L., Havukainen S., Koivistoinen O., Toivari M. Biotechnological production of glycolic acid and ethylene glycol: current state and perspectives. Applied Microbiology and Biotechnology. 2019. 103: 2525. https://doi.org/10.1007/s00253-019-09640-2.

Cotellessa C., Peris K., Chimenti S. Glycolic acid and its use in dermatology. Journal of the European Academy of Dermatology and Venereology. 1995. 5: 215.

Ginjupalli K., Shavi G.V., Averineni R.K., Bhat, M., Udupa N., Upadhya N.P. Poly (α-hydroxy acid) based polymers: A review on material and degradation aspects. Polymer Degradation and Stability. 2017. 144: 520. https://doi.org/10.1016/j.polymdegradstab.2017.08.024

Jem K.J., Tan B., The Development and Challenges of Poly (lactic acid) and Poly (glycolic acid). Advanced Industrial and Engineering Polymer Research. 2020. 3: 60. ttps://doi.org/10.1016/j.aiepr.2020.01.002.

https://www.grandviewresearch.com/press-release/global-glycolic-acid-market.

https://www.marketsandmarkets.com/Market-Reports/glycolic-polyglycolic-acid. Published Date: Oct 2019.

US Patent 2152852 Process for manufacture of glycolic acid. Loder D.J., du Pont deNemours& Company. USA - publ.04.04.1939.

US Patent 5723662 Process for preparing a particularly pure glycolic acid. Ebmeyer F., et al., Hoechst Actiengesellshaft, Germany – publ.03.03.1998.

US Patent 3867440 Process for the preparation of glycolic acid. Kobetz P., Ethyl Corporation, USA- publ.18.02.1975.

US Patent 6416980 B1 Method for producing glycolic acid from glyconitrile using nitrilase. Chauhan S. et al., du Pont de Nemours & Company. USA - publ.09.07.2002.

US Patent 7638617 B2. Enzymatic production of glycolic acid. DiCosimo R. et al., du Pont deNemours& Company. USA, publ.29.12.2009.

US Patent 7368492 B2 Process for the synthesis of glyconitrile. Foo T. et al. du Pont deNemours& Company. USA. - publ.06.05.2008.

Mattioda G., Blanc A. Glyoxal. Ullman’s encyclopedia of industrial chemistry. 2012. 17: 83. Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimDOI:10.1002/14356007.a12_491.pub2.

Balat M., Balat M., Kirtay E., Balat H.Main routes for the thermo-conversion of biomass into fuels and chemicals. Part 1: Pyrolysis systems. Energy Conversion and Management 2009. 50: 3147.

Dapsens P. Y., Mondelli C., Kusema B. T., Verel R., Pérez-Ramírez J. A continuous process for glyoxal valorisation using tailored Lewis-acid zeolite catalysts // Green Chem. – 2014. 16: 1176. DOI: 10.1039/c3gc42353k.

Tanabe K. Solid Acids and Bases: Their Catalytic Properties; Academic Press: New York, NY, USA; London, UK, 1970. 5. ISBN 0-12-683250-1.

Varvarin A.M., Levytska S.I., Glushchuk Ya.R., Brei V.V. Vapor-phase synthesis of lactide from ethyl lactate over TiO2/SiO2 catalyst. Ukrainian Chemistry journal. 2019. 85 (7): 31.

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. doi:10.3390/colloids301001

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